Use of zirconium compound to improve low speed pre-ignition performance

ABSTRACT

A lubricating oil composition, and a method of reducing LSPI events employing the lubricating oil composition, including a base oil of lubricating viscosity, and an additive composition including: one or more overbased calcium-containing detergent(s) sufficient to provide at least 500 ppmw of calcium, and a zirconium-containing nanoparticle(s) and/or one or more zirconium-containing compound(s) sufficient to provide greater than 0 ppmw to 6000 ppmw of zirconium, wherein the nanoparticles have a size of from 1 to 500 nm, as measured by Dynamic Light Scattering, an amount of one or more molybdenum-containing compound present in an amount sufficient to provide no greater than 100 ppmw of molybdenum, and wherein the additive composition has a weight ratio of ppmw of zirconium provided by the zirconium-containing nanoparticle(s) and/or the one or more zirconium-containing compound(s) to the ppmw of calcium provided by the one or more overbased-calcium-containing detergent(s) of greater than about 0.01 to less than 5.

TECHNICAL FIELD

The disclosure relates to lubricating oil compositions for reducing low-speed pre-ignition (LSPI) events in a boosted internal combustion engine. More specifically, the disclosure relates to a lubricating oil composition comprising an additive composition including an amount of one or more overbased calcium-containing detergent(s), and an amount of zirconium-containing nanoparticles and/or one or more zirconium-containing compound(s).

BACKGROUND

Boosted spark-ignited internal combustions engines such as turbocharged or supercharged internal combustion engines may exhibit an abnormal combustion phenomenon known as stochastic pre-ignition or low-speed pre-ignition (or “LSPI”). LSPI is a pre-ignition event that may include very high pressure spikes, early combustion during an inappropriate crank angle, and knock. All of these, individually and in combination, have the potential to cause degradation and/or severe damage to the engine.

Pre-ignition is a form of combustion that results in ignition in the combustion chamber prior to the desired ignition of the air-fuel mixture by the igniter. Pre-ignition has typically been a problem during high speed engine operation since heat from operation of the engine may heat a part of the combustion chamber to a sufficient temperature to ignite the air-fuel mixture upon contact. This type of pre-ignition is sometimes referred to as hot-spot pre-ignition.

More recently, intermittent abnormal combustion has been observed in boosted internal combustion engines at low speeds and medium-to-high loads. For example, during operation of the engine at 3,000 rpm or less, under load, with a brake mean effective pressure (BMEP) of at least 1,000 kPa, low-speed pre-ignition (LSPI) may occur in a random and stochastic fashion. During low speed engine operation, the compression stroke time is longest.

International Publication no. WO 2017/147380 A1 relates to lubricating oil compositions comprising an oil soluble metal compound, wherein the metal of the oil soluble metal compound may be a group (IV) metal for reducing low speed pre-ignition events in a spark-ignited direct injection internal combustion engine. WO 2017/147380 A1 exemplifies lubricating oil compositions containing titanium.

SUMMARY AND TERMS

The disclosure relates to a lubricating oil composition including greater than 50 wt. % of a base oil of lubricating viscosity, and an additive composition including one or more overbased calcium-containing detergent(s) and zirconium-containing nanoparticles and/or one or more zirconium-containing compound(s).

The following sentences describe some embodiments of the invention.

1. In a first aspect, the present invention relates to a lubricating oil composition comprising:

-   greater than 50 wt. % of a base oil of lubricating viscosity, and

an additive composition comprising:

-   -   an amount of one or more overbased calcium-containing         detergent(s) having a total base number of greater than 225 mg         KOH/g, measured by the method of ASTM D-2896 sufficient to         provide at least 500 ppmw of calcium to the lubricating oil         composition, based on a total weight of the lubricating oil         composition, and     -   an amount of zirconium-containing nanoparticle(s) and/or one or         more zirconium-containing compound(s) sufficient to provide         greater than 0 ppmw to 6000 ppmw of zirconium to the lubricating         oil composition, based on the total weight of the lubricating         oil composition, wherein the nanoparticles have a size of from 1         to 500 nm, as measured by Dynamic Light Scattering,     -   an amount of one or more molybdenum-containing compound present         in an amount sufficient to provide no greater than 100 ppmw of         molybdenum, based on a total weight of the lubricating oil         composition, and     -   wherein the additive composition has a weight ratio of ppmw of         zirconium provided by the zirconium-containing nanoparticle(s)         and/or the one or more zirconium-containing compound(s) to the         ppmw of calcium provided by the one or more         overbased-calcium-containing detergent(s) of greater than about         0.01 to less than 5; from about 600 ppmw to about 1000 ppmw of         phosphorus, based on the total weight of the lubricating oil         composition; and a total sulfated ash content of no greater than         1.5 wt. %, as measured by ASTM D874, based on the total weight         of the lubricating oil composition.

-   2. The lubricating oil composition of sentence 1, wherein the     lubricating oil composition may be effective to reduce low speed     pre-ignition events in a boosted internal combustion engine     lubricated with the lubricating oil composition relative to a number     of low speed pre-ignition events in the same engine lubricated with     reference lubricating oil R-1; or the reduction of LSPI events is     50% or greater reduction and the LSPI events are LSPI counts during     25,000 engine cycles, wherein the engine is operated at 2000     revolutions per minute with brake mean effective pressure of 1,800     kPa,     -   wherein R-1 is formulated from about 80.7 wt. % of a Group III         base oil, 12.1 wt. % of passenger car motor oil additive package         and 7.2 wt. % of a 35 SSI ethylene/propylene copolymer viscosity         index improver, wherein the passenger car motor oil additive         package is an API SN, ILSAC-GF-5, and ACEA A5/B5 qualified DI         package and R-1 also showed the following properties and partial         elemental analysis:

10.9 Kinematic Viscosity at 100° C., (mm²/sec) 3.3 HTHS at 150° C., (cP) 2438 calcium (ppmw) <10 magnesium (ppmw) 80 molybdenum (ppmw) 772 phosphorus (ppmw) 855 zinc (ppmw) 9.0 Total Base Number ASTM D-2896 (mg KOH/g) 165 Viscosity Index

-   3. The lubricating oil composition of any one of sentences 1-2,     wherein the one or more overbased calcium-containing detergent(s)     may have a total base number of greater than 250 mg KOH/g or more as     measured by the method of ASTM D-2896. -   4. The lubricating oil composition of any one of sentences 1-3,     wherein the weight ratio of the ppmw of zirconium provided by the     zirconium-containing nanoparticles and/or one or more     zirconium-containing compound(s) to the ppmw of calcium provided by     the one or more overbased calcium-containing detergent(s) may be     from 0.02 to 4, or from 0.03 to 3, or from 0.04 to 2.75. -   5. The lubricating oil composition of any one of sentences 1-4,     wherein the lubricating oil composition may contain greater than 1     ppmw of boron, or greater than 5 ppmw of boron, or greater than 10     ppmw of boron, or greater than 30 ppmw of boron to the lubricating     oil composition, based on the total weight of the lubricating oil     composition. -   6. The lubricating oil composition of any one of sentences 1-5,     wherein the one or more overbased calcium-containing detergent(s)     may be present in an amount to provide at least 600 ppmw of calcium     to less than 3000 ppmw calcium, or from 700 ppmw of calcium to less     than 2800 ppmw of calcium, or from 800 ppmw of calcium to less than     2500 ppmw of calcium, or from 2000 ppmw of calcium to 3500 ppmw of     calcium, or from 2100 ppmw of calcium to 3500 ppmw of calcium, or     from 2100 ppmw of calcium to 3100 ppmw of calcium to the lubricating     oil composition, based on the total weight of the lubricating oil     composition. -   7. The lubricating oil composition of any one of sentences 1-6,     wherein the zirconium-containing nanoparticle(s) and/or one or more     zirconium-containing compound(s) may be present in an amount to     provide at least 5 ppmw zirconium, or at least 50 ppmw zirconium, or     at least 75 ppmw zirconium, or from 75 ppmw zirconium to less than     2400 ppmw zirconium, or from 200 ppmw zirconium to less than 2400     ppmw zirconium, or from 400 ppmw zirconium to less than 2000 ppmw     zirconium to the lubricating oil composition, based on the total     weight of the lubricating oil composition. -   8. The lubricating oil composition of any one of sentences 1-7, may     further comprise one or more magnesium-containing detergents present     in an amount sufficient to provide greater than 500 ppmw to less     1000 ppmw of magnesium to the lubricating oil composition, based on     the total weight of the lubricating oil composition. -   9. The lubricating oil composition of sentence 8, wherein the one or     more magnesium-containing detergents may comprise an overbased     magnesium sulfonate detergent having a total base number of greater     than 225 mg KOH/g, as measured by the method of ASTM D-2896. -   10. The lubricating oil composition of any one of sentences 1-9,     wherein the one or more zirconium-containing compound(s) may be     selected from zirconium (IV) oxides, zirconium (IV) sulfides,     zirconium (IV) nitrates, zirconium (IV) alkoxides, zirconium     phenates, zirconium carboxylates, zirconium salicylates, zirconium     sulfonates, zirconium halides, and mixtures thereof. -   11. The lubricating oil composition of sentence 10, wherein the one     or more zirconium-containing compound(s) may be a zirconium     carboxylate, wherein the carboxylate group comprising from 3 to 20     carbon atoms, or from 4 to 15 carbon atoms, or from 6 to 10 carbon     atoms. -   12. The lubricating oil composition of sentence 11, wherein the     zirconium carboxylate may be selected from the group consisting of     zirconium 2-ethylhexanoate, zirconium isooctanoate, zirconium     isononanoate, zirconium isobutyrate, zirconium neopentanoate,     zirconium neooctanoate, zirconium neononanoate, zirconium     neodecanoate, and zirconium naphthenate. -   13. The lubricating oil composition of any one of sentences 1-9,     wherein the one or more zirconium-containing compound(s) may     comprise an organometallic zirconium compound. -   14. The lubricating oil composition of any one of sentences 1-9,     wherein the lubricating oil composition may comprise an amount of     zirconium-containing nanoparticles. -   15. The lubricating oil compositions of sentence 14, wherein the     zirconium-containing nanoparticles may be zirconium dioxide. -   16. The lubricating oil composition of any one of sentences 1-15,     wherein the total sulfated ash content is less than 1.2 wt. %, or     less than 1.0 wt. %, or less than 0.8 wt. %, or more than 0.5 wt. %     to less than 0.8 wt. % or more than 0.6 wt. % to less than 0.8 wt.     %, each as measured by ASTM D874. -   17. The lubricating oil composition of any one of sentences 1-16,     wherein the additive composition may provide from about less than     900 ppmw of phosphorus, or less than 800 ppmw of phosphorus, based     on the total weight of the lubricating oil composition. -   18. The lubricating oil composition of any one of sentences 1-17,     wherein the lubricating oil composition may be an engine oil     composition. -   19. In a second aspect, the present invention relates to methods for     reducing low-speed pre-ignition events in a boosted internal     combustion engine comprising:

lubricating a boosted internal combustion engine with a lubricating oil composition comprising greater than 50 wt. % of a base oil of lubricating viscosity and an additive composition comprising

an amount of one or more overbased calcium-containing detergent(s) having a total base number of greater than 225 mg KOH/g, measured by the method of ASTM D-2896 sufficient to provide at least 500 ppmw of calcium to the lubricating oil composition, based on a total weight of the lubricating oil composition, and

an amount of one or more zirconium-containing nanoparticles(s) and/or zirconium-containing compounds sufficient to provide greater than 0 ppmw to 6000 ppmw of zirconium to the lubricating oil composition, based on the total weight of the lubricating oil composition, wherein the nanoparticles have a size of from 1 to 500 nm, as measured by Dynamic Light Scattering,

at least one molybdenum-containing compound present in an amount sufficient to provide no greater than 100 ppmw of molybdenum, based on a total weight of the lubricating oil composition, and

wherein the additive composition has a weight ratio of the ppmw of zirconium provided by the zirconium-containing nanoparticles and/or one or more zirconium-containing compound(s) to the ppmw of calcium provided by the one or more overbased calcium-containing detergent(s) of greater than about 0.01 to less than 5, and

the lubricating oil composition contains from about 600 ppmw to about 1000 ppmw of phosphorus, based on the total weight of the lubricating oil composition; and a total sulfated ash content of no greater than 1.5 wt. %, as measured by ASTM D874, based on the total weight of the lubricating oil composition; and

operating the engine lubricated with the lubricating oil composition.

-   20. The method of sentence 19, wherein the method may be effective     to reduce low speed pre-ignition events in a boosted internal     combustion engine lubricated with the lubricating oil composition     relative to a number of low speed pre-ignition events in the same     engine lubricated with reference lubricating oil R-1; or the     reduction of LSPI events is 50% or greater reduction and the LSPI     events are LSPI counts during 25,000 engine cycles, wherein the     engine is operated at 2,000 revolutions per minute with brake mean     effective pressure of 1,800 kPa,

wherein R-1 is formulated from about 80.7 wt. % of a Group III base oil, 12.1 wt. % of passenger car motor oil additive package and 7.2 wt. % of a 35 SSI ethylene/propylene copolymer viscosity index improver, wherein the passenger car motor oil additive package is an API SN, ILSAC-GF-5, and ACEA A5/B5 qualified DI package and R-1 also showed the following properties and partial elemental analysis:

10.9 Kinematic Viscosity at 100° C., (mm²/sec) 3.3 HTHS at 150° C., (cP) 2438 calcium (ppmw) <10 magnesium (ppmw) 80 molybdenum (ppmw) 772 phosphorus (ppmw) 855 zinc (ppmw) 9.0 Total Base Number ASTM D-2896 (mg KOH/g) 165 Viscosity Index

-   21. The method of any one of sentences 19-20, wherein the one or     more overbased calcium-containing detergent(s) may have a total base     number of greater than 250 mg KOH/g or more as measured by the     method of ASTM D-2896. -   22. The method of any one of sentences 19-21, wherein the weight     ratio of the ppmw of zirconium provided by the zirconium-containing     nanoparticles and/or one or more zirconium-containing compound(s) to     the ppmw of calcium provided by the one or more overbased     calcium-containing detergent(s) may be from 0.02 to 4, or from 0.03     to 3, or from 0.04 to 2.75. -   23. The method of any one of sentences 19-22, wherein the     lubricating oil composition contains greater than 1 ppmw of boron,     or greater than 5 ppmw of boron, or greater than 10 ppmw of boron,     or greater than 30 ppmw of boron to the lubricating oil composition,     based on the total weight of the lubricating oil composition. -   24. The method of any one of sentences 19-23, wherein the one or     more overbased calcium-containing detergent(s) may be present in an     amount to provide at least 600 ppmw of calcium to less than 3000     ppmw calcium, or from 700 ppmw of calcium to less than 2800 ppmw of     calcium, or from 800 ppmw of calcium to less than 2500 ppmw of     calcium, or from 2000 ppmw of calcium to 3500 ppmw of calcium, or     from 2100 ppmw of calcium to 3500 ppmw of calcium, or from 2100 ppmw     of calcium to 3100 ppmw of calcium to the lubricating oil     composition, based on the total weight of the lubricating oil     composition. -   25. The method of any one of sentences 19-24, wherein the one or     more zirconium-containing nanoparticle(s) and/or the one or more     zirconium-containing compound(s) may be present in an amount to     provide at least 5 ppmw zirconium or at least 50 ppmw zirconium or     at least 75 ppmw zirconium, or from 75 ppmw zirconium to less than     2400 ppmw zirconium, or from 200 ppmw zirconium to less than 2400     ppmw zirconium, or from 400 ppmw zirconium to less than 2000 ppmw     zirconium to the lubricating oil composition, based on the total     weight of the lubricating oil composition. -   26. The method of any one of sentences 19-25, may further comprise     one or more magnesium-containing detergents present in an amount     sufficient to provide greater than 500 ppmw to less 1000 ppmw of     magnesium to the lubricating oil composition, based on the total     weight of the lubricating oil composition. -   27. The method of sentence 26, wherein the one or more     magnesium-containing detergents may include an overbased magnesium     sulfonate detergent having a total base number of greater than 225     mg KOH/g, as measured by the method of ASTM D-2896. -   28. The method of any one of sentences 19-27, wherein the one or     more zirconium-containing compound(s) may be selected from     zirconium (IV) oxides, zirconium (IV) sulfides, zirconium (IV)     nitrates, zirconium (IV) alkoxides, zirconium phenates, zirconium     carboxylates, zirconium salicylates, zirconium sulfonates, zirconium     halides, and mixtures thereof. -   29. The method of sentence 28, wherein the one or more     zirconium-containing compound(s) may be a zirconium carboxylate,     wherein the carboxylate group comprising from 3 to 20 carbon atoms,     or from 4 to 15 carbon atoms, or from 6 to 10 carbon atoms. -   30. The method of sentence 29, wherein the zirconium carboxylate may     be selected from the group consisting of zirconium 2-ethylhexanoate,     zirconium isooctanoate, zirconium isononanoate, zirconium     isobutyrate, zirconium neopentanoate, zirconium neooctanoate,     zirconium neononanoate, zirconium neodecanoate, and zirconium     naphthenate. -   31. The method of any one of sentences 19-27, wherein the one or     more zirconium-containing compound(s) may include an organometallic     zirconium compound or zirconium nanoparticles. -   32. The method of any one of sentences 19-31, wherein the total     sulfated ash content may be less than 1.2 wt. %, or less than 1.0     wt. %, or less than 0.8 wt. %, or more than 0.5 wt. % to less than     0.8 wt. % or more than 0.6 wt. % to less than 0.8 wt. %, each as     measured by ASTM D874. -   33. The method of any one of sentences 19-32, wherein the     lubricating oil composition may be an engine oil composition. -   34. The method of any one of sentences 19-33, wherein the additive     composition may provide from about less than 900 ppmw of phosphorus,     or less than 800 ppmw of phosphorus, based on the total weight of     the lubricating oil composition. -   35. The lubricating oil of any one of sentences 1-18, wherein the     maximum total metal from the zirconium provided by the     zirconium-containing nanoparticles and/or one or more     zirconium-containing compound(s) and calcium provided by the one or     more overbased calcium-containing detergent is less than 7545 ppmw;     or is up to 7510 ppmw; or is at least 950 ppmw to less than 7545     ppmw; or is at least 2350 ppmw to less than 7545 ppmw. -   36. The method of any one of sentences 19-34, wherein the maximum     total metal from the zirconium provided by the zirconium-containing     nanoparticles and/or one or more zirconium-containing compound(s)     and calcium provided by the one or more overbased calcium-containing     detergent is less than 7545 ppmw; or is up to 7510 ppmw; or is at     least 950 ppmw to less than 7545 ppmw; or is at least 2350 ppmw to     less than 7545 ppmw. -   37. The lubricating oil of any one of sentences 1 18 and 35, wherein     the one or more molybdenum-containing compounds is present in an     amount sufficient to contribute no greater than 80 ppmw molybdenum,     or no greater than 50 ppmw molybdenum, or no greater than 20 ppmw     molybdenum, or no greater than 15 ppmw, or greater than 0 ppmw     molybdenum, or greater than 5 ppmw molybdenum, or combinations     thereof, based on the total weight of the lubricating oil     composition. -   38. The method of any one of sentences 19 34 and 36, wherein the at     least one molybdenum-containing compounds is present in an amount     sufficient to contribute no greater than 80 ppmw molybdenum, or no     greater than 50 ppmw molybdenum, or no greater than 20 ppmw     molybdenum, or no greater than 15 ppmw, or greater than 0 ppmw     molybdenum, or greater than 5 ppmw molybdenum, or combinations     thereof, based on the total weight of the lubricating oil     composition.

The following definitions of terms are provided in order to clarify the meanings of certain terms as used herein.

The terms “oil composition,” “lubrication composition,” “lubricating oil composition,” “lubricating oil,” “lubricant composition,” “lubricating composition,” “fully formulated lubricant composition,” “lubricant,” “crankcase oil,” “crankcase lubricant,” “engine oil,” “engine lubricant,” “motor oil,” and “motor lubricant” are considered synonymous, fully interchangeable terminology referring to the finished lubrication product comprising a major amount of a base oil plus a minor amount of an additive composition.

As used herein, the terms “additive package,” “additive concentrate,” “additive composition,” “engine oil additive package,” “engine oil additive concentrate,” “crankcase additive package,” “crankcase additive concentrate,” “motor oil additive package,” “motor oil concentrate,” are considered synonymous, fully interchangeable terminology referring the portion of the lubricating oil composition excluding the major amount of base oil stock mixture. The additive package may or may not include the viscosity index improver or pour point depressant.

The term “overbased” relates to metal salts, such as metal salts of sulfonates, carboxylates, salicylates, and/or phenates, wherein the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level in excess of 100% (i.e., they may comprise more than 100% of the theoretical amount of metal needed to convert the acid to its “normal,” “neutral” salt). The expression “metal ratio,” often abbreviated as MR, is used to designate the ratio of total chemical equivalents of metal in the overbased salt to chemical equivalents of the metal in a neutral salt according to known chemical reactivity and stoichiometry. In a normal or neutral salt, the metal ratio is one and in an overbased salt, MR, is greater than one. They are commonly referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, salicylates, and/or phenols.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from hydrocarbon substituents, and substituted hydrocarbon substituents containing one or more of halo groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen and nitrogen, and wherein no more than two non-hydrocarbon substituents are present for every ten carbon atoms in the hydrocarbyl group.

As used herein, the term “hydrocarbylene substituent” or “hydrocarbylene group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group that is directly attached at two locations of the molecule to the remainder of the molecule by a carbon atom and having predominantly hydrocarbon character. Each hydrocarbylene group is independently selected from divalent hydrocarbon substituents, and substituted divalent hydrocarbon substituents containing halo groups, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen and nitrogen, and wherein no more than two non-hydrocarbon substituents is present for every ten carbon atoms in the hydrocarbylene group.

As used herein, the term “percent by weight”, unless expressly stated otherwise, means the percentage the recited component represents to the weight of the entire composition.

The terms “soluble,” “oil-soluble,” or “dispersible” used herein may, but does not necessarily, indicate that the compounds or additives are soluble, dissolvable, miscible, or capable of being suspended in the oil in all proportions. The foregoing terms do mean, however, that they are, for instance, soluble, suspendable, dissolvable, or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.

The term “TBN” as employed herein is used to denote the Total Base Number in mg KOH/g as measured by the method of ASTM D2896 or ASTM D4739 or DIN 51639-1.

The term “alkyl” as employed herein refers to straight, branched, cyclic, and/or substituted saturated chain moieties of from about 1 to about 100 carbon atoms.

The term “alkenyl” as employed herein refers to straight, branched, cyclic, and/or substituted unsaturated chain moieties of from about 3 to about 10 carbon atoms.

The term “aryl” as employed herein refers to single and multi-ring aromatic compounds that may include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and/or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.

Lubricants, combinations of components, or individual components of the present description may be suitable for use in various types of internal combustion engines. Suitable engine types may include, but are not limited to heavy duty diesel, passenger car, light duty diesel, medium speed diesel, or marine engines. An internal combustion engine may be a diesel fueled engine, a gasoline fueled engine, a natural gas fueled engine, a bio-fueled engine, a mixed diesel/biofuel fueled engine, a mixed gasoline/biofuel fueled engine, an alcohol fueled engine, a mixed gasoline/alcohol fueled engine, a compressed natural gas (CNG) fueled engine, or mixtures thereof. A diesel engine may be a compression ignited engine. A gasoline engine may be a spark-ignited engine. An internal combustion engine may also be used in combination with an electrical or battery source of power. An engine so configured is commonly known as a hybrid engine. The internal combustion engine may be a 2-stroke, 4-stroke, or rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland marine), aviation piston engines, low-load diesel engines, and motorcycle, automobile, locomotive, and truck engines.

The internal combustion engine may contain components of one or more of an aluminum-alloy, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composites, and/or mixtures thereof. The components may be coated, for example, with a diamond-like carbon coating, a lubrited coating, a phosphorus-containing coating, molybdenum-containing coating, a graphite coating, a nano-particle-containing coating, and/or mixtures thereof. The aluminum-alloy may include aluminum silicates, aluminum oxides, or other ceramic materials. In one embodiment the aluminum-alloy is an aluminum-silicate surface. As used herein, the term “aluminum alloy” is intended to be synonymous with “aluminum composite” and to describe a component or surface comprising aluminum and another component intermixed or reacted on a microscopic or nearly microscopic level, regardless of the detailed structure thereof. This would include any conventional alloys with metals other than aluminum as well as composite or alloy-like structures with non-metallic elements or compounds such with ceramic-like materials.

The lubricating oil composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulfur, phosphorus, or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant may be about 1 wt % or less, or about 0.8 wt % or less, or about 0.5 wt % or less, or about 0.3 wt % or less, or about 0.2 wt % or less. In one embodiment the sulfur content may be in the range of about 0.001 wt % to about 0.5 wt %, or about 0.01 wt % to about 0.3 wt %. The phosphorus content may be about 0.2 wt % or less, or about 0.1 wt % or less, or about 0.085 wt % or less, or about 0.08 wt % or less, or even about 0.06 wt % or less, about 0.055 wt % or less, or about 0.05 wt % or less. In one embodiment the phosphorus content may be about 50 ppmw to about 1000 ppmw, or about 325 ppmw to about 850 ppmw. The total sulfated ash content may be about 1.5 wt % or less, or about 1.2 wt % or less, or about 1.0 wt % or less, or about 0.8 wt % or less. In one embodiment the sulfated ash content may be about 0.5 wt % to about 0.8 wt %, or more than 0.6 wt % to less than 0.8 wt. %. In another embodiment, the sulfur content may be about 0.4 wt % or less, the phosphorus content may be about 0.08 wt % or less, and the sulfated ash is about 1 wt % or less. In yet another embodiment the sulfur content may be about 0.3 wt % or less, the phosphorus content is about 0.05 wt % or less, and the sulfated ash may be about 0.8 wt % or less.

In one embodiment the lubricating oil composition is an engine oil, wherein the lubricating oil composition may have (i) a sulfur content of about 0.5 wt % or less, (ii) a phosphorus content of about 0.1 wt % or less, and (iii) a sulfated ash content of about 1.5 wt % or less.

In one embodiment the lubricating oil composition is suitable for a 2-stroke or a 4-stroke marine diesel internal combustion engine. In one embodiment the marine diesel combustion engine is a 2-stroke engine. In some embodiments, the lubricating oil composition is not suitable for a 2-stroke or a 4-stroke marine diesel internal combustion engine for one or more reasons, including but not limited to, the high sulfur content of fuel used in powering a marine engine and the high TBN required for a marine-suitable engine oil (e.g., above about 40 TBN in a marine-suitable engine oil).

In some embodiments, the lubricating oil composition is suitable for use with engines powered by low sulfur fuels, such as fuels containing about 1 to about 5% sulfur. Highway vehicle fuels contain about 15 ppmw sulfur (or about 0.0015% sulfur).

Low speed diesel typically refers to marine engines, medium speed diesel typically refers to locomotives, and high speed diesel typically refers to highway vehicles. The lubricating oil composition may be suitable for only one of these types or all.

Further, lubricants of the present description may be suitable to meet one or more industry specification requirements such as ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CF, CF-4, CH-4, CK-4, FA-4, CJ-4, CI-4 Plus, CI-4, API SG, SJ, SL, SM, SN, ACEA A1/B1, A2/B2, A3/B3, A3/B4, A5/B5, C1, C2, C3, C4, C5, E4/E6/E7/E9, Euro 5/6,JASO DL-1, Low SAPS, Mid SAPS, or original equipment manufacturer specifications such as DexosTM 1, DexosTM 2, MB-Approval 229.1, 229.3, 229.5, 229.51/229.31, 229.52, 229.6, 229.71, 226.5, 226.51, 228.0/.1, 228.2/.3, 228.31, 228.5, 228.51, 228.61, VW 501.01, 502.00, 503.00/503.01, 504.00, 505.00, 505.01, 506.00/506.01, 507.00, 508.00, 509.00, 508.88, 509.99, BMW Longlife-01, Longlife-01 FE, Longlife-04, Longlife-12 FE, Longlife-14 FE+, Longlife-17 FE+, Porsche A40, C30, Peugeot Citroen Automobiles B71 2290, B71 2294, B71 2295, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Renault RN0700, RN0710, RN0720, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, WSS-M2C913-D, WSS-M2C948-B, WSS-M2C948-A, GM 6094-M, Chrysler MS-6395, Fiat 9.55535 G1, G2, M2, N1, N2, Z2, 51, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122 or any past or future PCMO or HDD specifications not mentioned herein. In some embodiments for passenger car motor oil (PCMO) applications, the amount of phosphorus in the finished fluid is 1000 ppmw or less or 900 ppmw or less or 800 ppmw or less.

Other hardware may not be suitable for use with the disclosed lubricant. A “functional fluid” is a term which encompasses a variety of fluids including but not limited to tractor hydraulic fluids, power transmission fluids including automatic transmission fluids, continuously variable transmission fluids and manual transmission fluids, hydraulic fluids, including tractor hydraulic fluids, some gear oils, power steering fluids, fluids used in wind turbines, compressors, some industrial fluids, and fluids related to power train components. It should be noted that within each of these fluids such as, for example, automatic transmission fluids, there are a variety of different types of fluids due to the various transmissions having different designs which have led to the need for fluids of markedly different functional characteristics. This is contrasted by the term “lubricating fluid” which is not used to generate or transfer power.

With respect to tractor hydraulic fluids, for example, these fluids are all-purpose products used for all lubricant applications in a tractor except for lubricating the engine. These lubricating applications may include lubrication of gearboxes, power take-off and clutch(es), rear axles, reduction gears, wet brakes, and hydraulic accessories.

When the functional fluid is an automatic transmission fluid, the automatic transmission fluids must have enough friction for the clutch plates to transfer power. However, the friction coefficient of fluids has a tendency to decline due to the temperature effects as the fluid heats up during operation. It is important that the tractor hydraulic fluid or automatic transmission fluid maintain its high friction coefficient at elevated temperatures, otherwise brake systems or automatic transmissions may fail. This is not a function of an engine oil.

Tractor fluids, and for example Super Tractor Universal Oils (STUOs) or Universal Tractor Transmission Oils (UTTOs), may combine the performance of engine oils with transmissions, differentials, final-drive planetary gears, wet-brakes, and hydraulic performance While many of the additives used to formulate a UTTO or a STUO fluid are similar in functionality, they may have deleterious effect if not incorporated properly. For example, some anti-wear and extreme pressure additives used in engine oils can be extremely corrosive to the copper components in hydraulic pumps. Detergents and dispersants used for gasoline or diesel engine performance may be detrimental to wet brake performance Friction modifiers specific to quiet wet brake noise, may lack the thermal stability required for engine oil performance Each of these fluids, whether functional, tractor, or lubricating, are designed to meet specific and stringent manufacturer requirements.

The present disclosure provides novel lubricating oil blends formulated for use as automotive crankcase lubricants. The present disclosure provides novel lubricating oil blends formulated for use as 2T and/or 4T motorcycle crankcase lubricants. Embodiments of the present disclosure may provide lubricating oils suitable for crankcase applications and having improvements in the following characteristics: air entrainment, alcohol fuel compatibility, antioxidancy, antiwear performance, biofuel compatibility, foam reducing properties, friction reduction, fuel economy, preignition prevention, rust inhibition, sludge and/or soot dispersability, piston cleanliness, deposit formation, and water tolerance.

Engine oils of the present disclosure may be formulated by the addition of one or more additives, as described in detail below, to an appropriate base oil formulation. The additives may be combined with a base oil in the form of an additive package (or concentrate) or, alternatively, may be combined individually with a base oil (or a mixture of both). The fully formulated engine oil may exhibit improved performance properties, based on the additives added and their respective proportions.

Additional details and advantages of the disclosure will be set forth in part in the description which follows, and/or may be learned by practice of the disclosure. The details and advantages of the disclosure may be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure, as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the LSPI test results for a lubricating oil composition with varying zirconium to calcium weight ratios.

FIG. 2 shows the average LSPI frequency for a high-calcium baseline engine oil formulation and another engine oil formulation demonstrating that the addition of zirconia nanoparticles to a high-calcium baseline engine oil formulation reduced the average number of LSPI events.

DETAILED DESCRIPTION

Various embodiments of the disclosure provide a lubricating oil composition and methods for reducing low speed pre-ignition. The lubricating oil composition may be useful in compression (diesel) engines and/or spark-ignited (gasoline) engines. In particular, engines in which the lubricating oil composition may be employed may include boosted internal combustion engines such as turbocharged and supercharged internal combustion engines. The boosted internal combustion engines include spark-ignited, direct injection and/or port-fuel injection engines. Preferably, the boosted internal combustion engine is a spark-ignited internal combustion engine or a direct injection engine.

In one aspect, the disclosure relates to lubricating oil compositions formulated for reducing the number of low speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition. The lubricating oil composition includes:

greater than 50 wt. % of a base oil of lubricating viscosity, and

an additive composition including:

an amount of one or more overbased calcium-containing detergent(s) having a total base number of greater than 225 mg KOH/g, measured by the method of ASTM D-2896 sufficient to provide at least 500 ppmw calcium to the lubricating oil composition, based on a total weight of the lubricating oil composition, and

an amount of zirconium nanoparticles and/or one or more zirconium-containing compound(s) sufficient to provide greater than 0 ppmw to 6000 ppmw of zirconium to the lubricating oil composition, based on the total weight of the lubricating oil composition,

at least one of a molybdenum-containing compound present in an amount sufficient to provide no greater than 100 ppmw of molybdenum, based on a total weight of the lubricating oil composition, and

wherein the additive composition has a weight ratio of ppmw of zirconium provided by the one or more zirconium-containing compound(s) to the ppmw of calcium provided by the one or more overbased-calcium-containing detergent(s) of greater than about 0.01 to less than 5; from about 600 ppmw to about 1000 ppmw of phosphorus, based on the total weight of the lubricating oil composition; and a total sulfated ash content of no greater than 1.5 wt. %, as measured by ASTM D874, based on the total weight of the lubricating oil composition.

The lubricating oil composition of the disclosure, including the additive composition, can reduce the number of low speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition relative to a number of low speed pre-ignition events in the same engine lubricated with a same lubricating oil composition with reference lubricating oil R-1, which the features of R-1 are discussed below.

Base Oil

The base oil used in the lubricating oil compositions may be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows:

Base oil Saturates Viscosity Category Sulfur (%) (%) Index Group I >0.03 and/or <90 80 to 120 Group II ≤0.03 and ≥90 80 to 120 Group III ≤0.03 and ≥90 ≥120 Group IV All polyalphaolefins (PAOs) Group V All others not included in Groups I, II, III, or IV

Groups I, II, and III are mineral oil process stocks. Group IV base oils contain true synthetic molecular species, which are produced by polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and/or polyphenyl ethers, and the like, but may also be naturally occurring oils, such as vegetable oils. It should be noted that although Group III base oils are derived from mineral oil, the rigorous processing that these fluids undergo causes their physical properties to be very similar to some true synthetics, such as PAOs. Therefore, oils derived from Group III base oils may be referred to as synthetic fluids in the industry. Group II+may comprise high viscosity index Group II.

The base oil used in the disclosed lubricating oil composition may be a mineral oil, animal oil, vegetable oil, synthetic oil, synthetic oil blends, or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined, and re-refined oils, and mixtures thereof.

Unrefined oils are those derived from a natural, mineral, or synthetic source without or with little further purification treatment. Refined oils are similar to the unrefined oils except that they have been treated in one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like. Oils refined to the quality of an edible may or may not be useful. Edible oils may also be called white oils. In some embodiments, lubricating oil compositions are free of edible or white oils.

Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often these oils are additionally processed by techniques directed to removal of spent additives and oil breakdown products.

Mineral oils may include oils obtained by drilling or from plants and animals or any mixtures thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.

Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(1-hexenes), poly(1-octenes), trimers or oligomers of 1-decene, e.g., poly(1-decenes), such materials being often referred to as a-olefins, and mixtures thereof; alkyl-benzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.

The major amount of base oil included in a lubricating composition may be selected from the group consisting of Group I, Group II, a Group III, a Group IV, a Group V, and a combination of two or more of the foregoing, and wherein the major amount of base oil is other than base oils that arise from provision of additive components or viscosity index improvers in the composition. In another embodiment, the major amount of base oil included in a lubricating composition may be selected from the group consisting of Group II, a Group III, a Group IV, a Group V, and a combination of two or more of the foregoing, and wherein the major amount of base oil is other than base oils that arise from provision of additive components or viscosity index improvers in the composition.

The amount of the oil of lubricating viscosity present may be the balance remaining after subtracting from 100 wt. % the sum of the amount of the performance additives inclusive of viscosity index improver(s) and/or pour point depressant(s) and/or other top treat additives. For example, the oil of lubricating viscosity that may be present in a finished fluid may be a major amount, such as greater than about 50 wt. %, greater than about 60 wt. %, greater than about 70 wt. %, greater than about 80 wt. %, greater than about 85 wt. %, or greater than about 90 wt. %.

The Overbased Calcium-Containing Detergent

The additive composition may include an amount of one or more overbased calcium-containing detergent(s) having a total base number of greater than 225 mg KOH/g, measured by the method of ASTM D-2896 sufficient to provide at least 500 ppmw calcium to the lubricating oil composition, based on a total weight of the lubricating oil composition.

Suitable detergent substrates include phenates, sulfur containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphorus acids, mono- and/or di-thiophosphoric acids, alkyl phenols, sulfur coupled alkyl phenol compounds, or methylene bridged phenols. Suitable detergents and their methods of preparation are described in greater detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and references cited therein. A suitable detergent may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylarylsulfonic acids with the aryl group being benzyl, tolyl, and xylyl.

Overbased detergents are well known in the art and may be alkali or alkaline earth metal overbased detergents. Such detergents may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, for example, an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

The terminology “overbased” relates to metal salts, such as metal salts of sulfonates, carboxylates, and phenates, wherein the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level in excess of 100% (i.e., they may comprise more than 100% of the theoretical amount of metal needed to convert the acid to its “normal,” “neutral” salt). The expression “metal ratio”, often abbreviated as MR, is used to designate the ratio of total chemical equivalents of metal in the overbased salt to chemical equivalents of the metal in a neutrals salt according to known chemical reactivity and stoichiometry. In a normal or neutral salt, the metal ratio is 1 and in an overbased salt or low based salt, MR, is greater than 1. They are commonly referred to as overbased, hyberbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

The overbased calcium-containing detergent may have a TBN of greater than about 225 mg KOH/gram or greater, or a TBN of about 250 mg KOH/gram or greater, or a TBN of about 300 mg KOH/gram or greater, of a TBN of about 350 mg KOH/gram or greater, or a TBN of about 375 mg KOH/gram or greater, or a TBN of about 400 mg KOH/gram or greater, as measured by the method of ASTM D-2896.

Examples of suitable overbased calcium-containing detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphorus acids, overbased calcium mono- and/or di-thiophosphoric acids, overbased calcium alkyl phenols, overbased calcium sulfur coupled alkyl phenol compounds, or overbased calcium methylene bridged phenols. Preferably, the one or more overbased calcium-containing detergent(s) is selected from an overbased calcium sulfonate detergent, an overbased calcium phenate detergent, and an overbased calcium salicylate detergent. Even more preferably, the overbased calcium-containing detergent is an overbased calcium sulfonate detergent.

The overbased calcium-containing detergent may have a metal to substrate ratio of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1 or from 12:1.

In some embodiments, the one or more overbased calcium-containing detergent is present in an amount sufficient to provide at least 500 ppmw calcium, or at least 600 ppmw of calcium to less than 3000 ppmw calcium, or from about 700 ppmw of calcium to less than 2800 ppmw of calcium, or from about 800 ppmw of calcium to less than about 2500 ppmw of calcium to the lubricating oil composition, or from 2000 ppmw of calcium to 3500 ppmw of calcium, or from 2100 ppmw of calcium to 3500 ppmw of calcium, or from 2100 ppmw of calcium to 3100 ppmw of calcium, based on the total weight of the lubricating oil composition.

In some embodiments, the additive composition has a weight ratio of ppmw of zirconium provided by the zirconium-containing nanoparticles and/or the one or more zirconium-containing compound(s) to the ppmw of calcium provided by the one or more overbased calcium-containing detergent(s) of greater than about 0.01 to less than 5, or from about 0.02 to about 4, or from about 0.03 to about 3, or from about 0.04 to 2.75.

In some embodiments, the additive composition has a weight ratio of the ppmw of calcium provided by the one or more overbased calcium-containing detergent(s) to the ppmw of zirconium provided by the zirconium-containing nanoparticles and/or the one or more zirconium-containing compound(s) of greater than about 0.1 to less than 500, or from about 0.2 to about 480.

Zirconium-Containing Nanoparticles/Zirconium-Containing Compound

The additive composition may include an amount of zirconium-containing nanoparticles and/or one or more zirconium-containing compound(s) sufficient to provide greater than 0 ppmw to 6000 ppmw of zirconium to the lubricating oil composition, based on the total weight of the lubricating oil composition. In other words, the lubricating oil composition may have greater than 0 ppmw to 6000 ppmw of zirconium provided by an amount of: a) zirconium-containing nanoparticles; b) one or more zirconium-containing compound(s); or c) an amount of zirconium-containing nanoparticles and one or more zirconium-containing compound(s).

The zirconium-containing compounds are preferably oil soluble or dispersible in the oil (e.g. nanoparticles) and may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or have more than one of these functions. In certain embodiments the inclusion of zirconium in the lubricating oil composition by use of one or more zirconium-containing compounds unexpectedly reduces the number of LSPI events and hence the LSPI Ratio.

The zirconium-containing compound may be in the form of elemental zirconium, organozirconium, zirconium oxide, sulphur-containing organozirconium, sulphur- and phosphorus-free zirconium sources, and the like. Other examples of suitable zirconium-containing compounds may include zirconium carboxylates, zirconium phenates, zirconium alkoxides, zirconium aminic compounds, zirconium sulfonates, zirconium salicylates, zirconium di-ketones, zirconium crown ethers, and the like. Other than the sulfonates, the zirconium-containing compound may contain phosphorus and sulfur or may be substantially devoid of phosphorous, or substantially devoid of sulfur, or substantially devoid of phosphorus and sulfur. By “substantially devoid of phosphorous” is meant that the nanoparticles/compounds, when formulated into lubricant formulations, deliver less than 0.12 weight percent of phosphorous to the finished lubricant formulation, and, more preferably, deliver less than 0.08 weight percent of phosphorous to the finished lubricant formulation. This applies at least to the antioxidant and the friction modifier. By “substantially devoid of sulfur” is meant that the nanoparticles/compounds, when formulated into lubricant formulations, deliver less than 0.7 weight percent of sulfur to the finished lubricant formulation, and, more preferably, deliver less than 0.4 weight percent of sulfur to the finished lubricant formulation. This applies at least to the antioxidant and the friction modifier. The compounds may contain from about 3 to about 200 or more carbon atoms in a hydrocarbyl component of the compound.

In some embodiments, the zirconium-containing compound may be selected from zirconium 2-ethylhexanoate, zirconium octoate, zirconium acetylacetonate, zirconium butoxide, zirconium dibutoxide, zirconium tert-butoxide, bis(cyclopentadienyl)zirconium dihydride, zirconium propoxide, zirconium ethoxide, alkylated zirconium salicylate, alkylated zirconium phenate, alkylated zirconium sulfonate, zirconium salts, and the like. Illustrative zirconium salts include, for example, zirconium oleate, zirconium stearate, zirconium palmitate, zirconium laurate, and the like

Examples of metal oxygenates include, but are not limited to, C₁-C₂₀ alkyl zirconates, such as the metal complexes, esters or reaction products of ethylene glycol, propylene glycol, octylene glycol, butanol, polybutanol, isopropanol, nonyl alcohol, 2-ethylhexanol, and iso-octyl alcohol. Aryl and aralkyl esters of zirconium may also be used such as tetraphenyl esters, tetrabenzyl esters, diethyl diphenyl esters, and the like of zirconium.

Zirconium complex or reaction products of carboxylic acids may also be used. Such compounds may be made by reacting an alkali metal salt hydrate or aqueous solution of an organic acid, the amine salt hydrate or aqueous solution of the organic acid, and/or the ammonium salt hydrate or aqueous solution of the organic acid with the aqueous solution of metal halide and subsequently oxidizing the reaction product.

Other zirconium organic compounds that may be used include, but are not limited to metal phenates, metal salicylates, metal phosphates, metal sulfonates, and sulphurized metal phenates, wherein each aromatic group has one or more aliphatic groups to impart hydrocarbon solubility. For example, in the metal sulfonates, each sulphonic acid moiety is attached to an aromatic nucleus which in turn usually contains one or more aliphatic substituents.

The metal salt of an alkylphenol or sulfurized alkylphenol is referred to as a neutral salt or soap. The metal used to neutralize the alkylphenol or sulfurized alkylphenol can be titanium, manganese, zirconium or any of the other commonly used metals such as calcium, sodium, magnesium and barium oxides and hydroxides etc. Accordingly, the sulfonates, salicylates, phosphates, and phenates described above may include sodium, potassium, calcium, and/or magnesium sulfonates, salicylates, phosphates, and phenates in combination with the zirconium sulfonates, salicylates, phosphates, and phenates. The highly basic salts of phenols or sulphurized phenols are often referred to as “overbased” phenates or “overbased sulphurized” phenates. For example, zirconium may be incorporated in a detergent additive as a carbonate salt arising from overbasing the detergent.

Other hydrocarbon soluble metal compounds may include dispersants, detergents, viscosity index improvers, antiwear additives, and other antioxidant compounds that are reacted to contain zirconium. For example, an ethylene copolymer or polyisobutylene based succinimide, Mannich or oil soluble dispersant additive, as described below, may be reacted with a metal alkoxide or any other suitable metal containing reagent to provide a metal containing dispersant.

Preferably, the one or more zirconium containing compounds is selected from zirconium (IV) oxides, zirconium (IV) sulfides, zirconium (IV) nitrates, zirconium (IV) alkoxides, zirconium phenates, zirconium carboxylates, zirconium salicylates, zirconium sulfonates, zirconium halides, and mixtures thereof. Preferably, the one or more zirconium containing compounds is a zirconium carboxylate. The carboxylate group can comprise from 3 to 20 carbon atoms, or from 4 to 15 carbon atoms, or from 6 to 10 carbon atoms. The zirconium carboxylate can be synthesized using a metal alkoxide such zirconium propoxide which is reacted with a carboxylic acid. Examples of metal carboxylates include, but are not limited to, zirconium products of the following carboxylic acids: formic, acetic, proprionic, butyric, pentanoic, hexanoic, heptanoic, octanoic, nonanoic, decanoic, dodecanoic, valeric, caproic, caprylic, lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, cyclohexanecarboxylic, phenylacetic, benzoic, and neodecanoic acids. The carboxylic acid can be substituted with one to three C₁-C₅ alkyl groups. Preferably, the zirconium carboxylate contains one to three tertiary carbons in each carboxylate moiety, or one to two tertiary carbons in each carboxylate moiety, or one tertiary carbon in each carboxylate moiety such as in zirconium 2-ethylhexanoate.

In some embodiments, the one or more zirconium containing compound(s) comprise of an organometallic zirconium compound or zirconium nanoparticles.

In some embodiments, the present invention may include zirconium-containing nanoparticles, for example, various forms of zirconia (zirconium dioxide) or other particulate zirconium-containing compounds. Nanoparticles are defined as compounds having three external dimensions in the range of from 1 to 500 nm, or from 1 to 400 nm, or from 1 to 300 nm, or from 1 to 250 nm, as measured by Dynamic Light Scattering in accordance with ASTM E2490-09 (2015).

In some embodiments, the zirconium dioxide nanoparticles may be treated with surface treatment agents to form oil-soluble zirconium dioxide particles. Suitable surface treatment agents include those that are reactive with the hydroxyl groups along the surface of the surface of the particles. In some embodiments, suitable surface treatment agents include organosilanes. In some embodiments, suitable organosilanes include one organic substituent and three hydrolysable substitutents. Exemplary organosilanes include: [2-(3-cyclohexenyl) ethyl] trimethoxysilane, trimethoxy(7-octen-1-yl) silane, isooctyl trimethoxy-silane, N-(3-triethoxysilylpropyl) methoxyethoxyethoxyethyl carbamate, N-(3-triethoxysilylpropyl) methoxyethoxyethoxyethyl carbamate, 3-(methacryloyloxy)propyltrimethoxysilane, allyl trimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-(methacryloyloxy) propyltriethoxysilane, 3-(methacryloyloxy) propylmethyldimethoxysilane, 3-acryloyloxypropyl)methyldimethoxysilane, -9 -3-(methacryloyloxy)propyldimethylethoxysilane, 3-(methacryloyloxy) propyldimethylethoxysilane, vinyldimethylethoxysilane, phenyltrimethoxysilane, n-octyltrimethoxysilane, dodecyltrimethoxysilane, isooctyltrimethoxysilane octadecyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriphenoxysilane, vinyltri-tbutoxysilane, vinyltris-isobutoxysilane, vinyltriisopropenoxysilane, vinyltris(2-methoxyethoxy) silane, styrylethyltrimethoxysilane, mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Heptamethyl(2-ltris(2-methoxyethoxy)silyllethylltrisiloxane (as described in US 20030220204) polydimethylsiloxane, arylsilanes, including, e.g., substituted and unsubstituted arylsilanes, alkylsilanes, including, e.g., substituted and unsubstituted alkyl silanes, including, e.g., methoxy and hydroxy substituted alkyl silanes, and combinations of two or more of the foregoing.

Other suitable surface treatments for use with the zirconia dioxide particles include acrylic acid, methacrylic acid, oleic acid, stearic acid, dodecanoic acid, 2υ-(2-methoxyethoxylethoxyl acetic acid (MEEAA), betacarboxyethylacrylate, 2-(2-methoxyethosy)acetic acid, methoxyphenyl acetic acid, and combinations of two or more of the foregoing. In some embodiments, a silane surface modifier comprising a polyether chain may be used, such as Silquest A-1230.

In some embodiments, the zirconium-containing nanoparticles and/or one or more zirconium containing compound(s) is present in an amount to provide greater than 0 ppmw zirconium, or at least 5 ppmw zirconium, or at least 50 ppmw zirconium or at least 75 ppmw zirconium, or from 75 ppmw zirconium to less than 2400 ppmw zirconium, or from 200 ppmw zirconium to less than 2400 ppmw zirconium, or from 400 ppmw zirconium to less than 2000 ppmw zirconium to the lubricating oil composition, based on the total weight of the lubricating oil composition.

Molybdenum-Containing Component

The additive composition may include an amount of one or more molybdenum-containing compound(s) sufficient to provide no greater than 100 ppmw of molybdenum, based on a total weight of the lubricating oil composition.

The one or more molybdenum-containing compound(s) of the present invention are preferably oil-soluble. The one or more molybdenum-containing compound(s) may have the functional performance of an antiwear agent, an antioxidant, a friction modifier, or mixtures thereof. The one or more oil-soluble molybdenum-containing compound(s) may be selected from molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, a trinuclear organo-molybdenum compound, and/or mixtures thereof. The molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment the one or more oil-soluble molybdenum-containing compound(s) may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment the one or more oil-soluble molybdenum-containing compound(s) may be a molybdenum dithiocarbamate.

Suitable examples of molybdenum compounds which may be used include commercial materials sold under the trade names such as Molyvan 822™, Molyvan™ A, Molyvan 2000™ and Molyvan 855™ from R. T. Vanderbilt Co., Ltd., and Sakura-Lube™ S-165, S-200, S-300, 5-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. No. 5,650,381; US RE 37,363 E1; US RE 38,929 E1; and US RE 40,595 E1, incorporated herein by reference in their entireties. Preferably, the one or more molybdenum-containing compounds may be the reaction product of a fatty acid ester and molybdenum oxide. Preferably, the fatty acid ester has from 4 to 30 carbon atoms, or from 6 to 20 carbon atoms.

Additionally, the molybdenum compound may be an acidic molybdenum compound. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkaline metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCl₄, MoO₂Br₂, Mo₂O₃Cl₆, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, the compositions can be provided with molybdenum by molybdenum/sulfur complexes of basic nitrogen compounds as described, for example, in U.S. Pat. Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; and WO 94/06897, incorporated herein by reference in their entireties.

Another class of suitable organo-molybdenum compounds are trinuclear molybdenum compounds, such as those of the formula Mo₃S_(k)L_(n)Q_(z) and mixtures thereof, wherein S represents sulfur, L represents independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms may be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, herein incorporated by reference in its entirety. The one or more oil-soluble molybdenum-containing compound(s) may be present in an amount sufficient to provide no greater than 100 ppmw molybdenum, or no greater than 80 ppmw molybdenum, or no greater than 50 ppmw molybdenum, or no greater than 20 ppmw molybdenum, or no greater than 15 ppmw, or greater than 0 ppmw molybdenum, or greater than 5 ppmw molybdenum, or combinations thereof, based on the total weight of the lubricating oil composition.

In another embodiments, the invention may provide a lubricating composition that is free of or substantially free of molybdenum-containing compounds. For purpose herein, the term “free of or substantially free of” means no intentionally added amount of material is present in the compositions but does allow for minute (less than 10 ppm) amounts of molybdenum, which may be regarded as a contaminant.

The Magnesium-Containing Detergent

The additive composition may include an amount of one or more magnesium-containing detergent(s) present in an amount sufficient to provide greater than 500 ppmw to less than 1500 ppmw of magnesium to the lubricating oil composition, based on the total weight of the lubricating oil composition.

Suitable detergent substrates include phenates, sulfur containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphorus acids, mono- and/or di-thiophosphoric acids, alkyl phenols, sulfur coupled alkyl phenol compounds, or methylene bridged phenols. Suitable detergents and their methods of preparation are described in greater detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and references cited therein. A suitable detergent may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylarylsulfonic acids with the aryl group being benzyl, tolyl, and xylyl. Examples of suitable additional detergents include, but are not limited to, magnesium phenates, magnesium sulfur containing phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylic acids, magnesium phosphorus acids, magnesium mono- and/or di-thiophosphoric acids, magnesium alkyl phenols, magnesium sulfur coupled alkyl phenol compounds, magnesium methylene bridged phenols, sodium phenates, sodium sulfur containing phenates, sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates, sodium carboxylic acids, sodium phosphorus acids, sodium mono- and/or di-thiophosphoric acids, sodium alkyl phenols, sodium sulfur coupled alkyl phenol compounds, or sodium methylene bridged phenols.

Overbased and low-based detergents are well known in the art and may be alkali or alkaline earth metal overbased detergents. Such detergents may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, for example, an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

The terminology “overbased” or “low-based” relates to metal salts, such as metal salts of sulfonates, carboxylates, and phenates, wherein the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level in excess of 100% (i.e., they may comprise more than 100% of the theoretical amount of metal needed to convert the acid to its “normal,” “neutral” salt). The expression “metal ratio”, often abbreviated as MR, is used to designate the ratio of total chemical equivalents of metal in the overbased salt to chemical equivalents of the metal in a neutrals salt according to known chemical reactivity and stoichiometry. In a normal or neutral salt, the metal ratio is 1 and in an overbased salt or low based salt, MR, is greater than 1. They are commonly referred to as overbased, hyberbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

The overbased magnesium-containing detergent can have a TBN of greater 225 mg KOH/gram, or as further examples, a TBN of about 250 mg KOH/gram or greater, or a TBN of about 300 mg KOH/gram or greater, or a TBN of about 350 mg KOH/gram or greater, or a TBN of about 375 mg KOH/gram or greater, or a TBN of about 400 mg KOH/gram or greater.

Examples of suitable overbased magnesium-containing detergents include, but are not limited to, overbased magnesium phenates, overbased magnesium sulfur containing phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphorus acids, overbased magnesium mono- and/or di-thiophosphoric acids, overbased magnesium alkyl phenols, overbased magnesium sulfur coupled alkyl phenol compounds, or overbased magnesium methylene bridged phenols.

The overbased detergent may have a metal to substrate ratio of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1.

In some embodiments, a detergent is effective at reducing or preventing rust in an engine.

In some embodiments, the one or more magnesium-containing detergents includes a low-based/neutral magnesium-containing detergent having a TBN of up to 175 mg KOH/g, or up to 150 mg KOH/g or at least 5 mg KOH/g, or at least 25 mg KOH/g, or at least 50 KOH/g. In some embodiments, the low-based/neutral magnesium-containing detergent is selected from low-based/neutral magnesium phenate detergents, low-based/neutral magnesium sulfur containing phenate detergents, and low-based/neutral magnesium sulfonates. Preferably, the low-based/neutral magnesium-containing detergent is a low-based/neutral magnesium phenate detergent or a low-based/neutral magnesium sulfonate detergent.

The low-based/neutral magnesium detergent comprises at least 2.5 wt. % of the total detergent in the lubricating oil composition. In some embodiments, at least 4 wt. %, or at least 6 wt. %, or at least 8 wt. %, or at least 10 wt. % or at least 12 wt. % or at least 20 wt. % of the total detergent in the lubricating oil composition is a low-based/neutral detergent which may optionally be a low-based/neutral calcium-containing detergent.

In some embodiments, the one or more magnesium-containing detergents is present in an amount to provide greater than 500 ppmw of magnesium, or from 500 ppmw of magnesium to 1500 ppmw of magnesium, or from about 600 ppmw of magnesium to 1300 ppmw of magnesium, or from about 700 ppmw of magnesium to 1200 ppmw of magnesium, or from about 800 ppmw of magnesium to 1000 ppmw of magnesium to the lubricating oil composition, based on the total weight of the lubricating oil composition.

Boron-Containing Compounds

The additive composition may include an amount of one or more boron-containing compound(s).

Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Pat. No. 5,883,057.

The boron-containing compound, if present, can be present in the lubricating oil composition in an amount of about 8 wt %, about 0.01 wt % to about 7 wt %, about 0.05 wt % to about 5 wt %, or about 0.1 wt % to about 3 wt % based on the total weight of the lubricating oil composition.

In some embodiments of the invention, the one or more boron-containing compound(s) is present in an amount to provide greater than 1 ppmw of boron, or greater than 5 ppmw of boron, or greater than 10 ppmw of boron, or greater than 30 ppmw of boron to the lubricating oil composition, based on the total weight of the lubricating oil composition.

In some embodiments, the lubricating oil composition may have more than 0 ppmw of boron and a ratio of total metal from the detergent in ppmw to total boron in ppmw of more than 7.5, or more than 50, or more than 500.

The lubricating oil composition may also include one or more optional components selected from the various additives set forth below.

Antioxidants

The lubricating oil compositions herein also may optionally contain one or more antioxidants. Antioxidant compounds are known and include for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyl diphenylamine, di-nonyl diphenylamine, octyl diphenylamine, di-octyl diphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.

The hindered phenol antioxidant may contain a secondary butyl and/or a tertiary butyl group as a sterically hindering group. The phenol group may be further substituted with a hydrocarbyl group and/or a bridging group linking to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment the hindered phenol antioxidant may be an ester and may include, e.g., Irganox™ L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester and may include Ethanox™ 4716 available from Albemarle Corporation.

Useful antioxidants may include diarylamines and high molecular weight phenols. In an embodiment, the lubricating oil composition may contain a mixture of a diarylamine and a high molecular weight phenol, such that each antioxidant may be present in an amount sufficient to provide up to about 5%, by weight, based upon the final weight of the lubricating oil composition. In an embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5% diarylamine and about 0.4 to about 2.5% high molecular weight phenol, by weight, based upon the final weight of the lubricating oil composition.

Examples of suitable olefins that may be sulfurized to form a sulfurized olefin include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof and their dimers, trimers and tetramers are especially useful olefins. Alternatively, the olefin may be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester, such as, butyl acrylate.

Another class of sulfurized olefin includes sulfurized fatty acids and their esters. The fatty acids are often obtained from vegetable oil or animal oil and typically contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Often, the fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof. Fatty acids and/or ester may be mixed with olefins, such as α-olefins.

In another alternative embodiment the antioxidant composition also contains a molybdenum-containing antioxidant in addition to the phenolic and/or aminic antioxidants discussed above. When a combination of these three antioxidants is used, preferably the ratio of phenolic to aminic to molybdenum-containing is (0 to 2):(0 to 2):(0 to 1).

The one or more antioxidant(s) may be present in ranges about 0 wt % to about 20 wt %, or about 0.1 wt % to about 10 wt %, or about 1 wt % to about 5 wt %, of the lubricating oil composition.

Antiwear Agents

The lubricating oil compositions herein also may optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, a metal thiophosphate; a metal dialkyldithiophosphate; a phosphoric acid ester or salt thereof; a phosphate ester(s); a phosphite; a phosphorus-containing carboxylic ester, ether, or amide; a sulfurized olefin; thiocarbamate-containing compounds including, thiocarbamate esters, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl)disulfides; and mixtures thereof. A suitable antiwear agent may be a molybdenum dithiocarbamate. The phosphorus containing antiwear agents are more fully described in European Patent 612 839. The metal in the dialkyl dithio phosphate salts may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups may be at least 8. The antiwear agent may in one embodiment include a citrate.

The antiwear agent may be present in ranges including about 0 wt % to about 15 wt %, or about 0.01 wt % to about 10 wt %, or about 0.05 wt % to about 5 wt %, or about 0.1 wt % to about 3 wt % of the lubricating oil composition.

Additional Optional Detergents

The lubricating oil composition may further comprise one or more neutral and/or low based detergents, as well as overbased detergents other than the detergents discussed above. Suitable detergent substrates include phenates, sulfur containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphorus acids, mono- and/or di-thiophosphoric acids, alkyl phenols, sulfur coupled alkyl phenol compounds, or methylene bridged phenols. Suitable detergents and their methods of preparation are described in greater detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and references cited therein. The detergent substrate may be salted with an alkali or alkaline earth metal such as, but not limited to, calcium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is free of barium. A suitable detergent may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylarylsulfonic acids with the aryl group being benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenates, calcium sulfur containing phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylic acids, calcium phosphorus acids, calcium mono- and/or di-thiophosphoric acids, calcium alkyl phenols, calcium sulfur coupled alkyl phenol compounds, calcium methylene bridged phenols, sodium phenates, sodium sulfur containing phenates, sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates, sodium carboxylic acids, sodium phosphorus acids, sodium mono- and/or di-thiophosphoric acids, sodium alkyl phenols, sodium sulfur coupled alkyl phenol compounds, or sodium methylene bridged phenols.

Overbased detergent additives are well known in the art and may be alkali or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, for example, an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

The terminology “overbased” relates to metal salts, such as metal salts of sulfonates, carboxylates, and phenates, wherein the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level in excess of 100% (i.e., they may comprise more than 100% of the theoretical amount of metal needed to convert the acid to its “normal,” “neutral” salt). The expression “metal ratio,” often abbreviated as MR, is used to designate the ratio of total chemical equivalents of metal in the overbased salt to chemical equivalents of the metal in a neutral salt according to known chemical reactivity and stoichiometry. In a normal or neutral salt, the metal ratio is one and in an overbased salt, MR, is greater than one. They are commonly referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

An overbased detergent of the lubricating oil composition may have a total base number (TBN) of greater than 225 mg KOH/gram, or as further examples, about 250 mg KOH/gram or greater, or about 350 mg KOH/gram or greater, or about 375 mg KOH/gram or greater, or about 400 mg KOH/gram or greater.

The overbased detergent may have a metal to substrate ratio of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1.

The low-based/neutral detergent has a TBN of up to 175 mg KOH/g, or up to 150 mg KOH/g. The low-based/neutral detergent may include a calcium-containing detergent. The low-based neutral calcium-containing detergent may be selected from a calcium sulfonate detergent, a calcium phenate detergent and a calcium salicylate detergent. In some embodiments, the low-based/neutral detergent is a calcium-containing detergent or a mixture of calcium-containing detergents. In some embodiments, the low-based/neutral detergent is a calcium sulfonate detergent or a calcium phenate detergent.

The low-based/neutral detergent may comprise at least 2.5 wt. % of the total detergent of the lubricating oil composition. In some embodiments, at least 4 wt. %, or at least 6 wt. %, or at least 8 wt. %, or at least 10 wt. % or at least 12 wt. % or at least 20 wt. % of the total detergent in the lubricating oil composition is a low-based/neutral detergent which may optionally be a low-based/neutral calcium-containing detergent.

In certain embodiments, the one or more low-based/neutral detergents provide from about 50 to about 1000 ppmw calcium to the lubricating oil composition based on a total weight of the lubricating oil composition. In some embodiments, the one or more low-based/neutral calcium-containing detergents provide from 75 to less than 800 ppmw, or from 100 to 600 ppmw, or from 125 to 500 ppmw calcium to the lubricating oil composition based on a total weight of the lubricating oil composition.

In some embodiments, a detergent is effective at reducing or preventing rust in an engine.

Dispersant

The lubricating oil composition may optionally further comprise one or more dispersants or mixtures thereof. Dispersants are often known as ashless-type dispersants because, prior to mixing in a lubricating oil composition, they do not contain ash-forming metals and they do not normally contribute any ash when added to a lubricant. Ashless type dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimide with the number average molecular weight of the polyisobutylene substituent being in the range about 350 to about 50,000, or to about 5,000, or to about 3,000, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for instance in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The polyolefin may be prepared from polymerizable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically the imide formed from a polyamine, typically a poly(ethyleneamine)

Preferred amines are selected from polyamines and hydroxyamines Examples of polyamines that may be used include, but are not limited to, diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), and higher homologues such as pentaethylamine hexamine (PEHA), and the like.

A suitable heavy polyamine is a mixture of polyalkylene-polyamines comprising small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylene hexamine) but primarily oligomers with 6 or more nitrogen atoms, 2 or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. A heavy polyamine preferably includes polyamine oligomers containing 7 or more nitrogens per molecule and with 2 or more primary amines per molecule. The heavy polyamine comprises more than 28 wt. % (e.g. >32 wt. %) total nitrogen and an equivalent weight of primary amine groups of 120-160 grams per equivalent.

Suitable polyamines are commonly known as PAM and contain a mixture of ethylene amines where TEPA and pentaethylene hexamine (PEHA) are the major part of the polyamine, usually less than about 80%.

Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (an equivalent weight of 115 to 112 grams per equivalent of primary amine) and a total nitrogen content of about 33-34 wt. %. Heavier cuts of PAM oligomers with practically no TEPA and only very small amounts of PEHA but containing primarily oligomers with more than 6 nitrogens and more extensive branching, may produce dispersants with improved dispersancy.

In an embodiment the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene with a number average molecular weight in the range about 350 to about 50,000, or to about 5000, or to about 3000, as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

In some embodiments, polyisobutylene, when included, may have greater than 50 mol %, greater than 60 mol %, greater than 70 mol %, greater than 80 mol %, or greater than 90 mol % content of terminal double bonds. Such PIB is also referred to as highly reactive PIB (“HR-PIB”). HR-PIB having a number average molecular weight ranging from about 800 to about 5000, as determined by GPC, is suitable for use in embodiments of the present disclosure. Conventional PIB typically has less than 50 mol %, less than 40 mol %, less than 30 mol %, less than 20 mol %, or less than 10 mol % content of terminal double bonds.

An HR-PIB having a number average molecular weight ranging from about 900 to about 3000 may be suitable, as determined by GPC. Such HR-PIB is commercially available, or can be synthesized by the polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in U.S. Pat. No. 4,152,499 to Boerzel, et al. and U.S. Pat. No. 5,739,355 to Gateau, et al. When used in the aforementioned thermal ene reaction, HR-PIB may lead to higher conversion rates in the reaction, as well as lower amounts of sediment formation, due to increased reactivity. A suitable method is described in U.S. Pat. No. 7,897,696.

In one embodiment the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride (“PIB SA”). The PIB SA may have an average of between about 1.0 and about 2.0 succinic acid moieties per polymer.

The % actives of the alkenyl or alkyl succinic anhydride can be determined using a chromatographic technique. This method is described in column 5 and 6 in U.S. Pat. No. 5,334,321.

The percent conversion of the polyolefin is calculated from the % actives using the equation in column 5 and 6 in U.S. Pat. No. 5,334,321.

Unless stated otherwise, all percentages are in weight percent and all molecular weights are number average molecular weights determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (with a number average molecular weight of 180 to about 18,000 as the calibration reference).

In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride.

In one embodiment, the dispersant may be derived from olefin maleic anhydride copolymer. As an example, the dispersant may be described as a poly-PIBSA.

In an embodiment, the dispersant may be derived from an anhydride which is grafted to an ethylene-propylene copolymer.

A suitable class of nitrogen-containing dispersants may be derived from olefin copolymers (OCP), more specifically, ethylene-propylene dispersants which may be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can be reacted with the functionalized OCP are described in U.S. Pat. Nos. 7,485,603; 7,786,057; 7,253,231; 6,107,257; and 5,075,383; and/or are commercially available. Further details of the ethylene-alpha olefin copolymers and dispersants made therefrom may be found in PCT/US18/37116 filed at the U.S. Receiving Office, the disclosure of which is hereby incorporated by reference in its entirety.

One class of suitable dispersants may be Mannich bases. Mannich bases are materials that are formed by the condensation of a higher molecular weight, alkyl substituted phenol, a polyalkylene polyamine, and an aldehyde such as formaldehyde. Mannich bases are described in more detail in U.S. Pat. No. 3,634,515.

A suitable class of dispersants may be high molecular weight esters or half ester amides.

A suitable dispersant may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. U.S. Pat. Nos. 7,645,726; 7,214,649; and 8,048,831 are incorporated herein by reference in their entireties.

In addition to the carbonate and boric acids post-treatments both the compounds may be post-treated, or further post-treatment, with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003, hereby incorporated by reference. Such treatments include, treatment with:

Inorganic phosphorous acids or anhydrates (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980);

Organic phosphorous compounds (e.g., U.S. Pat. No. 3,502,677);

Phosphorous pentasulfides;

Boron compounds as already noted above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387);

Carboxylic acid, polycarboxylic acids, anhydrides and/or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,948,386);

Epoxides polyepoxiates or thioexpoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495);

Aldehyde or ketone (e.g., U.S. Pat. No. 3,458,530);

Carbon disulfide (e.g., U.S. Pat. No. 3,256,185);

Glycidol (e.g., U.S. Pat. No. 4,617,137);

Urea, thourea or guanidine (e.g., U.S. Pat. Nos. 3,312,619; 3,865,813; and British Patent GB 1,065,595);

Organic sulfonic acid (e.g., U.S. Pat. No. 3,189,544 and British Patent GB 2,140,811);

Alkenyl cyanide (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569);

Diketene (e.g., U.S. Pat. No. 3,546,243);

A diisocyanate (e.g., U.S. Pat. No. 3,573,205);

Alkane sultone (e.g., U.S. Pat. No. 3,749,695);

1,3-Dicarbonyl Compound (e.g., U.S. Pat. No. 4,579,675);

Sulfate of alkoxylated alcohol or phenol (e.g., U.S. Pat. No. 3,954,639);

Cyclic lactone (e.g., U.S. Pat. Nos. 4,617,138; 4,645,515; 4,668,246; 4,963,275; and 4,971,711);

Cyclic carbonate or thiocarbonate linear monocarbonate or polycarbonate, or chloroformate (e.g., U.S. Pat. Nos. 4,612,132; 4,647,390; 4,648,886; 4,670,170);

Nitrogen-containing carboxylic acid (e.g., U.S. Pat. 4,971,598 and British Patent GB 2,140,811);

Hydroxy-protected chlorodicarbonyloxy compound (e.g., U.S. Pat. No. 4,614,522);

Lactam, thiolactam, thiolactone or ditholactone (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460);

Cyclic carbonate or thiocarbonate, linear monocarbonate or plycarbonate, or chloroformate (e.g., U.S. Pat. Nos. 4,612,132; 4,647,390; 4,646,860; and 4,670,170);

Nitrogen-containing carboxylic acid (e.g., U.S. Pat. No. 4,971,598 and British Patent GB 2,440,811);

Hydroxy-protected chlorodicarbonyloxy compound (e.g., U.S. Pat. No. 4,614,522);

Lactam, thiolactam, thiolactone or dithiolactone (e.g., U.S. Pat. Nos. 4,614,603, and 4,666,460);

Cyclic carbamate, cyclic thiocarbamate or cyclic dithiocarbamate (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459);

Hydroxyaliphatic carboxylic acid (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318; 4,713,189);

Oxidizing agent (e.g., U.S. Pat. No. 4,379,064);

Combination of phosphorus pentasulfide and a polyalkylene polyamine (e.g., U.S. Pat. No. 3,185,647);

Combination of carboxylic acid or an aldehyde or ketone and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086; 3,470,098);

Combination of a hydrazine and carbon disulfide (e.g. U.S. Pat. No. 3,519,564);

Combination of an aldehyde and a phenol (e.g., U.S. Pat. Nos. 3,649,229; 5,030,249; 5,039,307);

Combination of an aldehyde and an O-diester of dithiophosphoric acid (e.g., U.S. Pat. No. 3,865,740);

Combination of a hydroxyaliphatic carboxylic acid and a boric acid (e.g., U.S. Pat. No. 4,554,086);

Combination of a hydroxyaliphatic carboxylic acid, then formaldehyde and a phenol (e.g., U.S. Pat. No. 4,636,322);

Combination of a hydroxyaliphatic carboxylic acid and then an aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,663,064);

Combination of formaldehyde and a phenol and then glycolic acid (e.g., U.S. Pat. No. 4,699,724);

Combination of a hydroxyaliphatic carboxylic acid or oxalic acid and then a diisocyanate (e.g. U.S. Pat. No.4,713,191);

Combination of inorganic acid or anhydride of phosphorus or a partial or total sulfur analog thereof and a boron compound (e.g., U.S. Pat. No. 4,857,214);

Combination of an organic diacid then an unsaturated fatty acid and then a nitrosoaromatic amine optionally followed by a boron compound and then a glycolating agent (e.g., U.S. Pat. No. 4,973,412);

Combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278);

Combination of an aldehyde and a triazole then a boron compound (e.g., U.S. Pat. No. 4,981,492);

Combination of cyclic lactone and a boron compound (e.g., U.S. Pat. No. 4,963,275 and 4,971,711). The above-mentioned patents are herein incorporated in their entireties.

The TBN of a suitable dispersant may be from about 10 to about 65 mg KOH/g dispersant, on an oil-free basis, which is comparable to about 5 to about 30 TBN if measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

The dispersant, if present, can be used in an amount sufficient to provide up to about 20 wt %, based upon the final weight of the lubricating oil composition. Another amount of the dispersant that can be used may be about 0.1 wt % to about 15 wt %, or about 0.1 wt % to about 10 wt %, or about 3 wt % to about 10 wt %, or about 1 wt % to about 6 wt %, or about 7 wt % to about 12 wt %, based upon the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more types of dispersants in any desired ratio may be used.

Friction Modifiers

The lubricating oil compositions herein also may optionally contain one or more friction modifiers. Suitable friction modifiers may comprise metal containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, amino guanidine, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil other naturally occurring plant or animal oils, dicarboxylic acid esters, esters or partial esters of a polyol and one or more aliphatic or aromatic carboxylic acids, and the like.

Suitable friction modifiers may contain hydrocarbyl groups that are selected from straight chain, branched chain, or aromatic hydrocarbyl groups or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon and hydrogen or hetero atoms such as sulfur or oxygen. The hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments the friction modifier may be a long chain fatty acid ester. In another embodiment the long chain fatty acid ester may be a mono-ester, or a di-ester, or a (tri)glyceride. The friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols and generally include a polar terminal group (e.g. carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless nitrogen-free friction modifier is known generally as glycerol monooleate (GMO) which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Pat. No. 6,723,685, herein incorporated by reference in its entirety.

Aminic friction modifiers may include amines or polyamines Such compounds can have hydrocarbyl groups that are linear, either saturated or unsaturated, or a mixture thereof and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines Such compounds may have hydrocarbyl groups that are linear, either saturated, unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

The amines and amides may be used as such or in the form of an adduct or reaction product with a boron compound such as a boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate. Other suitable friction modifiers are described in U.S. Pat. No. 6,300,291, herein incorporated by reference in its entirety.

A friction modifier may optionally be present in the lubricating oil composition in ranges such as about 0 wt % to about 10 wt %, or about 0.01 wt % to about 8 wt %, or about 0.1 wt % to about 4 wt %.

Transition Metal-Containing Compounds

In another embodiment, the oil-soluble compound may be a transition metal containing compound or a metalloid. The transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, and the like. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, and the like.

In an embodiment, an oil-soluble transition metal-containing compound may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions. In an embodiment the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as a titanium (IV) alkoxide. Among the titanium containing compounds that may be used in, or which may be used for preparation of the oils-soluble materials of, the disclosed technology are various Ti (IV) compounds such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes including but not limited to titanium phenates; titanium carboxylates such as titanium (IV) 2-ethyl-1-3-hexanedioate or titanium citrate or titanium oleate; and titanium (IV) (triethanolaminato)isopropoxide. Other forms of titanium encompassed within the disclosed technology include titanium phosphates such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzenesulfonates), or, generally, the reaction product of titanium compounds with various acid materials to form salts, such as oil-soluble salts. Titanium compounds can thus be derived from, among others, organic acids, alcohols, and glycols. Ti compounds may also exist in dimeric or oligomeric form, containing Ti—O—Ti structures. Such titanium materials are commercially available or can be readily prepared by appropriate synthesis techniques which will be apparent to the person skilled in the art. They may exist at room temperature as a solid or a liquid, depending on the particular compound. They may also be provided in a solution form in an appropriate inert solvent.

In one embodiment, the titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such materials may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl- (or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or it may be reacted with any of a number of materials, such as (a) a polyamine-based succinimide/amide dispersant having free, condensable —NH functionality; (b) the components of a polyamine-based succinimide/amide dispersant, i.e., an alkenyl- (or alkyl-) succinic anhydride and a polyamine, (c) a hydroxy-containing polyester dispersant prepared by the reaction of a substituted succinic anhydride with a polyol, aminoalcohol, polyamine, or mixtures thereof. Alternatively, the titanate-succinate intermediate may be reacted with other agents such as alcohols, aminoalcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product thereof either used directly to impart Ti to a lubricant, or else further reacted with the succinic dispersants as described above. As an example, 1 part (by mole) of tetraisopropyl titanate may be reacted with about 2 parts (by mole) of a polyisobutene-substituted succinic anhydride at 140-150° C. for 5 to 6 hours to provide a titanium modified dispersant or intermediate. The resulting material (30 g) may be further reacted with a succinimide dispersant from polyisobutene-substituted succinic anhydride and a polyethylenepolyamine mixture (127 grams +diluent oil) at 150° C. for 1.5 hours, to produce a titanium-modified succinimide dispersant.

Another titanium containing compound may be a reaction product of titanium alkoxide and C₆ to C₂₅ carboxylic acid. The reaction product may be represented by the following formula:

wherein n is an integer selected from 2, 3 and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or by the formula:

wherein m+n=4 and n ranges from 1 to 3, R₄ is an alkyl moiety with carbon atoms ranging from 1-8, Ri is selected from a hydrocarbyl group containing from about 6 to 25 carbon atoms, and R₂ and R₃ are the same or different and are selected from a hydrocarbyl group containing from about 1 to 6 carbon atoms, or by the formula:

wherein x ranges from 0 to 3, R₁ is selected from a hydrocarbyl group containing from about 6 to 25 carbon atoms, R₂, and R₃ are the same or different and are selected from a hydrocarbyl group containing from about 1 to 6 carbon atoms, and R₄ is selected from a group consisting of either H, or C₆ to C₂₅ carboxylic acid moiety.

Suitable carboxylic acids may include, but are not limited to caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

In an embodiment the oil soluble titanium compound may be present in the lubricating oil composition in an amount to provide from 0 to 3000 ppmw titanium or 25 to about 1500 ppmw titanium or about 35 ppmw to 500 ppmw titanium or about 50 ppmw to about 300 ppm.

Viscosity Index Improvers

The lubricating oil compositions herein also may optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene/propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, styrene/maleic ester copolymers, hydrogenated styrene/butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers and suitable examples are described in US Publication No. 20120101017A1.

The lubricating oil compositions herein also may optionally contain one or more dispersant viscosity index improvers in addition to a viscosity index improver or in lieu of a viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine; polymethacrylates functionalized with an amine, or esterified maleic anhydride-styrene copolymers reacted with an amine

The total amount of viscosity index improver and/or dispersant viscosity index improver may be about 0 wt % to about 20 wt %, about 0.1 wt % to about 15 wt %, about 0.1 wt % to about 12 wt %, or about 0.5 wt % to about 10 wt %, of the lubricating oil composition.

Other Optional Additives

Other additives may be selected to perform one or more functions required of a lubricating fluid. Further, one or more of the mentioned additives may be multi-functional and provide functions in addition to or other than the function prescribed herein.

A lubricating oil composition according to the present disclosure may optionally comprise other performance additives. The other performance additives may be in addition to specified additives of the present disclosure and/or may comprise one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swelling agents and mixtures thereof. Typically, fully-formulated lubricating oil will contain one or more of these performance additives.

Suitable metal deactivators may include derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.

Suitable foam inhibitors include silicon-based compounds, such as siloxane.

Suitable pour point depressants may include a polymethylmethacrylates or mixtures thereof. Pour point depressants may be present in an amount sufficient to provide from about 0 wt % to about 1 wt %, about 0.01 wt % to about 0.5 wt %, or about 0.02 wt % to about 0.04 wt % based upon the final weight of the lubricating oil composition.

Suitable rust inhibitors may be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids, such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimer and trimer acids, such as those produced from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000 and alkenylsuccinic acids in which the alkenyl group contains about 10 or more carbon atoms such as, tetrapropenylsuccinic acid, tetradecenylsuccinic acid, and hexadecenylsuccinic acid. Another useful type of acidic corrosion inhibitors are the half esters of alkenyl succinic acids having about 8 to about 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols. The corresponding half amides of such alkenyl succinic acids are also useful. A useful rust inhibitor is a high molecular weight organic acid. In some embodiments, an engine oil is devoid of a rust inhibitor.

The rust inhibitor, if present, can be used in an amount sufficient to provide about 0 wt % to about 5 wt %, about 0.01 wt % to about 3 wt %, about 0.1 wt % to about 2 wt %, based upon the final weight of the lubricating oil composition.

In general terms, a suitable lubricant may include additive components in the ranges listed in the following table.

TABLE 2 Wt. % Wt. % (Suitable (Suitable Component Embodiments) Embodiments) Dispersant(s)  0.1-20.0  1.0-10.0 Antioxidant(s) 0.1-5.0 0.01-3.0  Detergent(s)  0.1-15.0 0.2-8.0 Ashless TBN booster(s) 0.0-1.0 0.01-0.5  Corrosion inhibitor(s) 0.0-5.0 0.0-2.0 Molybdenum containing compound 0.1-1.0 0.20-0.55 Metal dihydrocarbyldithiophosphate(s) 0.1-6.0 0.1-4.0 Ash-free phosphorus compound(s) 0.0-6.0 0.0-4.0 Antifoaming agent(s) 0.0-5.0 0.001-0.15  Antiwear agent(s) 0.0-1.0 0.0-0.8 Pour point depressant(s) 0.0-5.0 0.01-1.5  Viscosity index improver(s) (on a  0.0-25.0  0.1-15.0 liquid/dilute basis) Dispersant viscosity index improver(s)  0.0-10.0 0.0-5.0 Friction modifier(s) 0.01-5.0  0.05-2.0  Base oil(s) Balance Balance Total 100 100

The percentages of each component above represent the weight percent of each component, based upon the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils.

Additives used in formulating the compositions described herein may be blended into the base oil individually or in various sub-combinations. However, it may be suitable to blend all of the components concurrently using an additive concentrate (i.e., additives plus a diluent, such as a hydrocarbon solvent).

EXAMPLES

The following examples are illustrative, but not limiting, of the methods and compositions of the present disclosure. Other suitable modifications and adaptations of the variety of conditions and parameters normally encountered in the field, and which are obvious to those skilled in the art, are within the spirit and scope of the disclosure. All patents and publications cited herein are fully incorporated by reference herein in their entirety.

Each of the lubricating oil compositions contained a major amount of a base oil and a base conventional dispersant inhibitor (DI) package. The DI package contained conventional amounts of dispersant(s), antiwear additive(s), antioxidant(s), friction modifier(s), antifoam agent(s), process oil(s), viscosity index improver(s), and pour point depressant(s), as set forth in Table 3. Specifically, the DI package contained a succinimide dispersant, a molybdenum-containing compound, an antioxidant, and an antifoam agent. The major amount of base oil was a mixture of Group III and Group IV base oils. The components that were varied are specified in the Tables and discussion of the Examples below. All the values listed are states as weight percent of the component in the lubricating oil compositions (i.e., active ingredient plus diluent oil, if any) unless specified otherwise.

TABLE 3 DI Package Composition Ranges Component Wt. % Antioxidant(s) 0.5 to 2.5 Antiwear agent(s), including any metal dihydrocarbyl 0.5 to 1.5 dithiophosphate Antifoaming agent(s) 0.001 to 0.05  Detergent(s) 1.0-2.0 Dispersant (s) 5.0-9.0 Metal-containing friction modifier(s) 0.03-1.5  Metal free friction modifier(s)  0 to 0.5 Pour point depressant(s) 0.05 to 0.5  Process oil 0.25 to 1.0  Viscosity Index Improver(s) 0.0 to 2.0

Sulfated ash (SASH) was calculated for total of metallic elements that contribute to SASH in the lubricant composition according to the following factors that were multiplied by the amount of each metallic element in the lubricant composition according to: http://konnaris.com/portals/0/search/calculations.htm.

Element Factor Barium 1.70 Boron 3.22 Calcium 3.40 Copper 1.252 Lead 1.464 Lithium 7.92 Magnesium 4.95 Manganese 1.291 Molybdenum 1.50 Potassium 2.33 Sodium 3.09 Zinc 1.50

Reference oil R-1 was formulated from about 80.7 wt. % of a Group III base oil, 12.1 wt. % of HiTEC® 11150 PCMO Additive Package available from Afton Chemical Corporation and 7.2 wt. % of a 35 SSI ethylene/propylene copolymer viscosity index improver. HiTEC® 11150 passenger car motor oil additive package is an API SN, ILSAC-GF-5, and ACEA A5/B5 qualified DI package. R-1 also showed the following properties and partial elemental analysis:

Reference Oil R-1 10.9 Kinematic Viscosity at 100° C., (mm²/sec) 3.3 HTHS at 150° C., (cP) 2438 calcium (ppmw) <10 magnesium (ppmw) 80 molybdenum (ppmw) 772 phosphorus (ppmw) 855 zinc (ppmw) 9.0 Total Base Number ASTM D-2896 (mg KOH/g) 165 Viscosity Index

Low Speed Pre-Ignition (LSPI) events were measured in a GM 2.0 Liter, 4 cylinder Ecotec turbocharged gasoline direct injection (TGDi) engine. One complete LSPI fired engine test consisted of 4 test cycles. Within a single test cycle, two operational stages or segments are repeated in order to generate LSPI events. In stage A, when LSPI is most likely to occur, the engine is operated at about 2000 rpm and about 1,800 kPa brake mean effective pressure (BMEP). In stage B, when LSPI is not likely to occur, the engine is operated at about 1500 rpm and about 1,700 kPa BMEP. For each stage, data is collected over 25,000 engine cycles. The structure of a test cycle is as follows: stage A stage A stage B stage B stage A stage A. Each stage is separated by an idle period. Because LSPI is statistically significant during stage A, the LSPI event data that was considered in the present examples only included LSPI events generated during stage A operation. Thus, for one complete LSPI fired engine test, data was typically generated over a total of 16 stages and was used to evaluate performance of comparative and inventive oils.

LSPI events were determined by monitoring peak cylinder pressure (PP) and when 2% of the combustible material in the combustion chamber burns (MFB02). The threshold for peak cylinder pressure is calculated for each cylinder and for each stage and is typically 65,000 to 85,000 kPa. The threshold for MFB02 is calculated for each cylinder and for each stage and typically ranges from about 3.0 to about 7.5 Crank Angle Degree (CAD) After Top Dead Center (ATDC). An LSPI was recorded when both the PP and MFB02 thresholds were exceeded in a single engine cycle. LSPI events can be reported in many ways. In order to remove ambiguity involved with reporting counts per engine cycle, where different fired engine tests can be conducted with a different number of engine cycles, the relative number of LSPI events of comparative and inventive oils were reported as an “LSPI Ratio”. In this way improvement relative to some standard response is clearly demonstrated.

In the examples carried out in Table 4, the LSPI Ratio was reported as a ratio of the LSPI events of a test oil relative to the LSPI events of Reference Oil “R-1”.

Considerable improvement in LSPI is recognized when there is greater than 50% reduction in LSPI events relative to R-1 (an LSPI Ratio of less than 0.5). A further improvement in LSPI is recognized when there is greater than 70% reduction in LSPI events (an LSPI Ratio of less than 0.3), an even further improvement in LSPI is recognized when there is greater than 75% reduction in LSPI events (an LSPI Ratio of less than 0.25), and an even further improvement in LSPI is recognized when there is greater than 80% reduction in LSPI events relative to R-1 (an LSPI Ratio of less than 0 20), and an even further improvement in LSPI is recognized when there is greater than 90% reduction in LSPI events relative to R-1 (an LSPI Ratio of less than 0.1). The LSPI Ratio for R-1 reference oil is thus deemed to be 1.00.

In the following examples, the LSPI Ratio was reported as a ratio of the LSPI events of a test oil relative to the LSPI events of Reference Oil “R-1”.

The following examples were prepared to demonstrate the LSPI performance of an amount of one or more Zr containing compounds in combination with an overbased calcium-containing detergent. Each of the examples contained a majority of a base oil, a base oil conventional DI package, and an overbased calcium-containing detergent. Inventive examples, IE 1-IE 3 also included a Zr containing compound. The LSPI results may be found in Table 4 and FIG. 1.

TABLE 4 LSPI Ca Zr Zirconium Ca/Zr Zr/Ca Perfor- (ppmw) (ppmw) type Ratio Ratio mance R-1 2438 0 N/A N/A N/A 1 IE 1 2454 926 Zirconium 2.7 0.38 0.5 2-Ethyl- hexanoate IE 2 2444 1872 Zirconium 1.3 0.77 0.23 2-Ethyl- hexanoate IE 3 2265 5245 Nano- 0.4 2.32 0.01 particles

R-1 did not include an amount of zirconium from zirconium-containing compounds or zirconium-containing nanoparticles. As seen from Table 4, examples IE-1 and IE-2 including 926 ppmw and 1872 ppmw of zirconium, respectively, show that with increased zirconium a reduction in LSPI performance is observed, relative to R-1. Furthermore, it was observed that employing zirconium-containing nanoparticles provided a significant reduction in LSPI events relative to R-1.

The following table shows prophetic examples according to the present invention.

TABLE 5 Zr Ca Ca/Zr Zr/Ca Sulfated (ppm) (ppm) Ratio Ratio LSPI Ash CE-1 0 ~2300 N/A N/A FAIL PASS IE-4 50 ~2300 46.00 0.02 IE-5 100 ~2300 23.00 0.04 IE-6 200 ~2300 11.50 0.09 IE-7 486 ~2300 4.73 0.21 PASS PASS IE-8 926 ~2300 2.48 0.40 PASS PASS IE-9 1872 ~2300 1.23 0.81 PASS PASS CE-2 5245 ~2300 0.44 2.28 PASS FAIL

The following table shows prophetic examples with predicted results for LSPI and Sulfated Ash.

TABLE 6 CE-3 IE-10 IE-11 IE-12 CE-4 Ca 900 900 900 900 900 Mg 900 900 900 900 900 P 600 600 600 600 600 Zn 636 636 636 636 636 B 40 40 40 40 40 Mo 10 10 10 10 10 Si 5 5 5 5 5 Zr 0 50 200 500 1000 Ca/Zr Ratio 0.00 18.00 4.50 1.80 0.90 Zr/Ca Ratio 0.00 0.06 0.22 0.56 1.11 Predicted LSPI 0.35 0.31 0.21 0.01 0 Sulfated Ash (calculated) 0.85 0.85 0.87 0.91 0.98 Relative LSPI (predicted) 1 0.89 0.60 0.03 0.00 SASH PASS PASS PASS PASS FAIL LSPI FAIL PASS PASS PASS PASS

Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the embodiments disclosed herein. As used throughout the specification and claims, “a” and/or “an” may refer to one or more than one. Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, percent, ratio, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about,” whether or not the term “about” is present. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.

The foregoing embodiments are susceptible to considerable variation in practice. Accordingly, the embodiments are not intended to be limited to the specific exemplifications set forth hereinabove. Rather, the foregoing embodiments are within the spirit and scope of the appended claims, including the equivalents thereof available as a matter of law.

The patentees do not intend to dedicate any disclosed embodiments to the public, and to the extent any disclosed modifications or alterations may not literally fall within the scope of the claims, they are considered to be part hereof under the doctrine of equivalents.

It is to be understood that each component, compound, substituent or parameter disclosed herein is to be interpreted as being disclosed for use alone or in combination with one or more of each and every other component, compound, substituent or parameter disclosed herein.

It is also to be understood that each amount/value or range of amounts/values for each component, compound, substituent or parameter disclosed herein is to be interpreted as also being disclosed in combination with each amount/value or range of amounts/values disclosed for any other component(s), compounds(s), substituent(s) or parameter(s) disclosed herein and that any combination of amounts/values or ranges of amounts/values for two or more component(s), compounds(s), substituent(s) or parameters disclosed herein are thus also disclosed in combination with each other for the purposes of this description.

It is further understood that each range disclosed herein is to be interpreted as a disclosure of each specific value within the disclosed range that has the same number of significant digits. Thus, a range of from 1-4 is to be interpreted as an express disclosure of the values 1, 2, 3 and 4.

It is further understood that each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compounds, substituent or parameter. Thus, this disclosure to be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range.

Furthermore, specific amounts/values of a component, compound, substituent or parameter disclosed in the description or an example is to be interpreted as a disclosure of either a lower or an upper limit of a range and thus can be combined with any other lower or upper limit of a range or specific amount/value for the same component, compound, substituent or parameter disclosed elsewhere in the application to form a range for that component, compound, substituent or parameter. 

1. A lubricating oil composition comprising: greater than 50 wt. % of a base oil of lubricating viscosity, and an additive composition comprising: an amount of one or more overbased calcium-containing detergent(s) having a total base number of greater than 225 mg KOH/g, measured by the method of ASTM D-2896 sufficient to provide at least 500 ppmw of calcium to the lubricating oil composition, based on a total weight of the lubricating oil composition, and an amount of zirconium-containing nanoparticle(s) and/or one or more zirconium-containing compound(s) sufficient to provide greater than 0 ppmw to 6000 ppmw of zirconium to the lubricating oil composition, based on the total weight of the lubricating oil composition, wherein the nanoparticles have a size of from 1 to 500 nm, as measured by Dynamic Light Scattering, an amount of one or more molybdenum-containing compound present in an amount sufficient to provide no greater than 100 ppmw of molybdenum, based on a total weight of the lubricating oil composition, and wherein the additive composition has a weight ratio of ppmw of zirconium provided by the zirconium-containing nanoparticle(s) and/or the one or more zirconium-containing compound(s) to the ppmw of calcium provided by the one or more overbased-calcium-containing detergent(s) of greater than about 0.01 to less than 5; from about 600 ppmw to about1000 ppmw of phosphorus, based on the total weight of the lubricating oil composition; and a total sulfated ash content of no greater than 1.5 wt. %, as measured by ASTM D874, based on the total weight of the lubricating oil composition.
 2. The lubricating oil composition of claim 1, wherein the lubricating oil composition is effective to reduce low speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition relative to a number of low speed pre-ignition events in the same engine lubricated with reference lubricating oil R-1; or the reduction of LSPI events is 50% or greater reduction and the LSPI events are LSPI counts during 25,000 engine cycles, wherein the engine is operated at 2000 revolutions per minute with brake mean effective pressure of 1,800 kPa, wherein R-1 is formulated from about 80.7 wt. % of a Group III base oil, 12.1 wt. % of passenger car motor oil additive package and 7.2 wt. % of a 35 SSI ethylene/propylene copolymer viscosity index improver, wherein the passenger car motor oil additive package is an API SN, ILSAC-GF-5, and ACEA A5/B5 qualified DI package and R-1 also showed the following properties and partial elemental analysis: 10.9 Kinematic Viscosity at 100° C., (mm²/sec) 3.3 HTHS at 150° C., (cP) 2438 calcium (ppmw) <10 magnesium (ppmw) 80 molybdenum (ppmw) 772 phosphorus (ppmw) 855 zinc (ppmw) 9.0 Total Base Number ASTM D-2896 (mg KOH/g) 165 Viscosity Index


3. The lubricating oil composition of claim 1, wherein the one or more overbased calcium-containing detergent(s) has a total base number of greater than 250 mg KOH/g or more as measured by the method of ASTM D-2896.
 4. The lubricating oil composition of claim 1, wherein the weight ratio of the ppmw of zirconium provided by the zirconium-containing nanoparticles and/or one or more zirconium-containing compound(s) to the ppmw of calcium provided by the one or more overbased calcium-containing detergent(s) is from 0.02 to
 4. 5. The lubricating oil composition of claim 1, wherein the lubricating oil composition contains greater than 1 ppmw of boron based on the total weight of the lubricating oil composition; or wherein the one or more overbased calcium-containing detergent(s) is present in an amount to provide at least 600 ppmw of calcium to less than 3000 ppmw calcium to the lubricating oil composition, based on the total weight of the lubricating oil composition.
 6. The lubricating oil composition of claim 1, wherein the zirconium-containing nanoparticle(s) and/or one or more zirconium-containing compound(s) is present in an amount to provide at least 5 ppmw zirconium to the lubricating oil composition, based on the total weight of the lubricating oil composition.
 7. The lubricating oil composition of claim 1, further comprising one or more magnesium-containing detergents present in an amount sufficient to provide greater than 500 ppmw to less 1000 ppmw of magnesium to the lubricating oil composition, based on the total weight of the lubricating oil composition; or wherein the one or more magnesium-containing detergents comprises an overbased magnesium sulfonate detergent having a total base number of greater than 225 mg KOH/g, as measured by the method of ASTM D-2896.
 8. The lubricating oil composition of claim 1, wherein the one or more zirconium-containing compound(s) is selected from zirconium (IV) oxides, zirconium (IV) sulfides, zirconium (IV) nitrates, zirconium (IV) alkoxides, zirconium phenates, zirconium carboxylates, zirconium salicylates, zirconium sulfonates, zirconium halides, and mixtures thereof.
 9. The lubricating oil composition of claim 8, wherein the one or more zirconium-containing compound(s) is a zirconium carboxylate, wherein the carboxylate group comprising from 3 to 20 carbon atoms.
 10. The lubricating oil composition of claim 9, wherein the zirconium carboxylate is selected from the group consisting of zirconium 2-ethylhexanoate, zirconium isooctanoate, zirconium isononanoate, zirconium isobutyrate, zirconium neopentanoate, zirconium neooctanoate, zirconium neononanoate, zirconium neodecanoate, and zirconium naphthenate; or wherein the one or more zirconium-containing compound(s) comprises an organometallic zirconium compound; or wherein the lubricating oil composition comprising an amount of zirconium-containing nanoparticles.
 11. The lubricating oil composition of claim 1, wherein the lubricating oil composition is an engine oil composition.
 12. A method for reducing low-speed pre-ignition events in a boosted internal combustion engine comprising: lubricating a boosted internal combustion engine with a lubricating oil composition comprising greater than 50 wt. % of a base oil of lubricating viscosity and an additive composition comprising an amount of one or more overbased calcium-containing detergent(s) having a total base number of greater than 225 mg KOH/g, measured by the method of ASTM D-2896 sufficient to provide at least 500 ppmw calcium to the lubricating oil composition, based on a total weight of the lubricating oil composition, and an amount of one or more zirconium-containing nanoparticles(s) and/or zirconium-containing compounds sufficient to provide greater than 0 ppmw to 6000 ppmw of zirconium to the lubricating oil composition, based on the total weight of the lubricating oil composition, wherein the nanoparticles have a size of from 1 to 500 nm, as measured by Dynamic Light Scattering, at least one molybdenum-containing compound present in an amount sufficient to provide no greater than 100 ppmw of molybdenum, based on a total weight of the lubricating oil composition, and wherein the additive composition has a weight ratio of the ppmw of zirconium provided by the zirconium-containing nanoparticles and/or one or more zirconium-containing compound(s) to the ppmw of calcium provided by the one or more overbased calcium-containing detergent(s) of greater than about 0.01 to less than 5, and the lubricating oil composition contains from about 600 ppmw to about 1000 ppmw of phosphorus, based on the total weight of the lubricating oil composition; and a total sulfated ash content of no greater than 1.5 wt. %, as measured by ASTM D874, based on the total weight of the lubricating oil composition; and operating the engine lubricated with the lubricating oil composition.
 13. The method of claim 12, wherein the method is effective to reduce low speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition relative to a number of low speed pre-ignition events in the same engine lubricated with reference lubricating oil R-1; or the reduction of LSPI events is 50% or greater reduction and the LSPI events are LSPI counts during 25,000 engine cycles, wherein the engine is operated at 2,000 revolutions per minute with brake mean effective pressure of 1,800 kPa, wherein R-1 is formulated from about 80.7 wt. % of a Group III base oil, 12.1 wt. % of passenger car motor oil additive package and 7.2 wt. % of a 35 SSI ethylene/propylene copolymer viscosity index improver, wherein the passenger car motor oil additive package is an API SN, ILSAC-GF-5, and ACEA A5/B5 qualified DI package and R-1 also showed the following properties and partial elemental analysis: 10.9 Kinematic Viscosity at 100° C., (mm²/sec) 3.3 HTHS at 150° C., (cP) 2438 calcium (ppmw) <10 magnesium (ppmw) 80 molybdenum (ppmw) 772 phosphorus (ppmw) 855 zinc (ppmw) 9.0 Total Base Number ASTM D-2896 (mg KOH/g) 165 Viscosity Index


14. The method of claim 12, wherein the one or more overbased calcium-containing detergent(s) has a total base number of greater than 250 mg KOH/g or more as measured by the method of ASTM D-2896.
 15. The method of claim 12, wherein the weight ratio of the ppmw of zirconium provided by the zirconium-containing nanoparticles and/or one or more zirconium-containing compound(s) to the ppmw of calcium provided by the one or more overbased calcium-containing detergent(s) is from 0.02 to
 4. 16. The method of claim 12, wherein the lubricating oil composition contains greater than 1 ppmw of boron based on the total weight of the lubricating oil composition; or wherein the one or more overbased calcium-containing detergent(s) is present in an amount to provide at least 600 ppmw of calcium to less than 3000 ppmw calcium to the lubricating oil composition, based on the total weight of the lubricating oil composition.
 17. The method of claim 12, wherein the zirconium-containing nanoparticles and/or the one or more zirconium-containing compound(s) is present in an amount to provide at least 5 ppmw zirconium to the lubricating oil composition, based on the total weight of the lubricating oil composition.
 18. The method of claim 12, further comprising one or more magnesium-containing detergents present in an amount sufficient to provide greater than 500 ppmw to less 1000 ppmw magnesium to the lubricating oil composition, based on the total weight of the lubricating oil composition; or wherein the one or more magnesium-containing detergents comprises an overbased magnesium sulfonate detergent having a total base number of greater than 225 mg KOH/g, as measured by the method of ASTM D-2896.
 19. The method of claim 12, wherein the one or more zirconium-containing compound(s) is selected from zirconium (IV) oxides, zirconium (IV) sulfides, zirconium (IV) nitrates, zirconium (IV) alkoxides, zirconium phenates, zirconium carboxylates, zirconium salicylates, zirconium sulfonates, zirconium halides, and mixtures thereof; or wherein the one or more zirconium-containing compound(s) comprises an organometallic zirconium compound or zirconium nanoparticles.
 20. The method of claim 12, wherein the lubricating oil composition is an engine oil composition. 